CN111247486A

CN111247486A - Method for manufacturing circuit substrate and method for manufacturing touch panel

Info

Publication number: CN111247486A
Application number: CN201880067544.6A
Authority: CN
Inventors: 松田知树; 片山晃男; 山田悟
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2017-10-19
Filing date: 2018-09-18
Publication date: 2020-06-05
Also published as: JP6995873B2; JPWO2019077924A1; TW201928534A; WO2019077924A1

Abstract

A method for manufacturing a circuit substrate and a method for manufacturing a touch panel sequentially include: forming a positive photosensitive composition layer on the conductive layer; pattern-exposing the positive photosensitive composition layer; developing the pattern-exposed positive photosensitive composition layer; etching the conductive layer using the developed positive photosensitive composition layer as a mask; a step of blanket-exposing the developed positive photosensitive composition layer; and removing the blanket-exposed positive photosensitive composition layer.

Description

Method for manufacturing circuit substrate and method for manufacturing touch panel

Technical Field

The present invention relates to a method for manufacturing a circuit board and a method for manufacturing a touch panel.

Background

For example, in a display device or the like (an organic Electroluminescence (EL) display device, a liquid crystal display device, or the like) including a touch panel such as a capacitive input device, circuit wirings such as an electrode pattern, an edge wiring portion, and a wiring for leading out a wiring portion of a sensor corresponding to a visual recognition portion are provided inside the touch panel.

In the formation of such patterned circuit wiring, the use of a dry film resist as a photosensitive transfer material has been studied for the reason that the number of steps for obtaining a desired pattern shape is small.

Specifically, the following methods are widely used: a photosensitive composition layer (layer of a photosensitive composition) is formed on a substrate using a dry film resist, the photosensitive composition layer is pattern-exposed through a mask having a pattern or the like, and the exposed photosensitive composition layer is developed to obtain a resist pattern, and then, the substrate is subjected to an etching treatment, thereby forming a circuit wiring.

For example, japanese patent application laid-open No. 2017-116611 discloses a positive photosensitive transfer material including a temporary support and a positive photosensitive resin layer disposed on the temporary support, the positive photosensitive resin layer including: a polymer containing a constituent unit represented by the following formula A and having a weight-average molecular weight of 100000 or less; a plasticizer having a weight average molecular weight smaller than that of the polymer containing the constituent unit represented by formula a; and a photoacid generator.

[ chemical formula 1]

In the formula A, R³¹And R³²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R³¹And R³²Is alkyl or aryl, R³³Represents alkyl or aryl, R³¹Or R³²Can be reacted with R³³Linked to form a cyclic ether, R³⁴Represents a hydrogen atom or a methyl group, X⁰Represents a single bond or an arylene group.

Disclosure of Invention

Technical problem to be solved by the invention

The present inventors have found that, in a conventional method for manufacturing a circuit board, when a removing solution for an etching mask is used for a long period of time, the removability may gradually decrease.

An object to be solved by the embodiments of the present invention is to provide a method for manufacturing a circuit board and a method for manufacturing a touch panel, which have excellent removal performance of an etching mask even when a removing liquid is used for a long time.

Means for solving the technical problem

The following means is included in the solution for solving the above-described problems.

< 1 > a method for manufacturing a circuit board, comprising in this order: forming a positive photosensitive composition layer on the conductive layer; pattern-exposing the positive photosensitive composition layer; developing the pattern-exposed positive photosensitive composition layer; etching the conductive layer using the developed positive photosensitive composition layer as a mask; a step of blanket-exposing the developed positive photosensitive composition layer; and removing the blanket-exposed positive photosensitive composition layer.

< 2 > the method for manufacturing a circuit board according to < 1 >, wherein,

the method for manufacturing a semiconductor device includes a step of heating the blanket-exposed positive photosensitive composition layer between the step of blanket-exposing the positive photosensitive composition layer and the step of removing the blanket-exposed positive photosensitive composition layer.

< 3 > the method for manufacturing a circuit board according to < 1 > or < 2 >, wherein,

in the step of removing the positive photosensitive composition layer, a removing liquid containing 30 mass% or more of water is used.

< 4 > the method for manufacturing a circuit substrate according to any one of < 1 > to < 3 >, wherein,

the positive photosensitive composition layer contains a polymer containing a constituent unit having an acid group protected by an acid-decomposable group, and a photoacid generator.

< 5 > the method for manufacturing a circuit board according to < 4 >, wherein,

the constituent unit having an acid group protected with an acid-decomposable group is a constituent unit represented by any of the following formulae a1 to A3.

[ chemical formula 2]

In the formula A1, R¹¹And R¹²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R¹¹And R¹²Is alkyl or aryl, R¹³Represents alkyl or aryl, R¹¹Or R¹²Can be reacted with R¹³Linked to form a cyclic ether, R¹⁴Represents a hydrogen atom or a methyl group, X¹Represents a single bond or a 2-valent linking group, R¹⁵Represents a substituent, and n represents an integer of 0 to 4.

In the formula A2, R²¹And R²²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R²¹And R²²Is alkyl or aryl, R²³Represents alkyl or aryl, R²¹Or R²²Can be reacted with R²³Linked to form a cyclic ether, R²⁴Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.

In the formula A3, R³¹And R³²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R³¹And R³²Is alkyl or aryl, R³³Represents alkyl or aryl, R³¹Or R³²Can be reacted with R³³Linked to form a cyclic ether, R³⁴Represents a hydrogen atom or a methyl group, X⁰Represents a single bond or a 2-valent linking group.

< 6 > the method for manufacturing a circuit board according to < 5 >, wherein,

the constituent unit having an acid group protected with an acid-decomposable group is a constituent unit represented by the formula a 3.

< 7 > the method of manufacturing a circuit board according to any one of < 1 > to < 6 >, wherein,

the conductive layer is at least 1 layer selected from the group consisting of a metal layer and a conductive metal oxide layer.

< 8 > the method for manufacturing a circuit substrate according to any one of < 1 > to < 7 >, wherein,

the conductive layer is a copper layer.

< 9 > the method for manufacturing a circuit substrate according to any one of < 1 > to < 8 >, wherein,

in the step of forming the positive photosensitive composition layer, a photosensitive transfer material having a temporary support and a positive photosensitive composition layer is used.

< 10 > the method for manufacturing a circuit board according to < 9 >, wherein,

the temporary support is a resin film.

< 11 > the method for manufacturing a circuit board according to < 9 > or < 10 >, wherein,

the temporary support comprises a cyclic olefin polymer.

< 12 > a method for manufacturing a touch panel, comprising the method for manufacturing a circuit substrate as defined in any one of < 1 > to < 11 >.

Effects of the invention

According to the embodiments of the present invention, it is possible to provide a method for manufacturing a circuit board and a method for manufacturing a touch panel, in which the etching mask is excellent in the removal property even when the removing liquid is used for a long time.

Drawings

Fig. 1 is a schematic view showing an example of a method for manufacturing a circuit board according to the present invention using a positive photosensitive transfer material.

Fig. 2 is a schematic diagram showing an example of the layer structure of the positive photosensitive transfer material preferably used in the present invention.

Fig. 3 is a schematic view showing pattern a.

Fig. 4 is a schematic view showing pattern B.

Detailed Description

The present invention will be described below. Note that, although the description is made with reference to the drawings, the reference numerals may be omitted.

In the present specification, the numerical range represented by "to" means a range including numerical values before and after "to" as a lower limit value and an upper limit value.

In the present specification, "(meth) acrylic acid" means both or either of acrylic acid and methacrylic acid, and "(meth) acrylate" means both or either of acrylate and methacrylate.

In the present specification, when a plurality of substances corresponding to each component are present in the composition, the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless otherwise specified.

The term "step" in the present specification means not only an independent step, but also includes a step that can achieve the intended purpose of the step even when it cannot be clearly distinguished from other steps.

In the present specification, the term "total solid content" refers to the total mass of components obtained by removing a solvent from all the components of the composition. The "solid component" refers to a component obtained by removing the solvent as described above, and may be a solid or liquid at 25 ℃.

In the expression of a group (atomic group) in the present specification, the expression not labeled with substituted and unsubstituted includes a group having no substituent and also includes a group having a substituent. For example, "alkyl" includes not only alkyl having no substituent (unsubstituted alkyl), but also alkyl having a substituent (substituted alkyl).

In addition, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.

In the present invention, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.

In the present invention, a combination of 2 or more preferred embodiments is a more preferred embodiment.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present invention are molecular weights obtained by detecting with a solvent THF (tetrahydrofuran) or a differential refractometer and converting with polystyrene as a standard substance by a Gel Permeation Chromatography (GPC) analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (trade names manufactured by TOSOH CORPORATION), unless otherwise specified.

(method of manufacturing Circuit Board)

The method for manufacturing a circuit board according to the present invention includes the steps of: forming a positive photosensitive composition layer on the conductive layer; pattern-exposing the positive photosensitive composition layer; developing the pattern-exposed positive photosensitive composition layer; etching the conductive layer using the developed positive photosensitive composition layer as a mask; a step of blanket-exposing the developed positive photosensitive composition layer; and removing the blanket-exposed positive photosensitive composition layer.

As a result of intensive studies, the present inventors have found that the method for producing a circuit board according to the present invention is excellent in the removal property of an etching mask even when a removing liquid (stripping liquid) is used for a long period of time. The details of the mechanism for obtaining the above-described effects are not clear, but are presumed as follows.

As described above, the present inventors have found that in a conventional method for manufacturing a circuit board, when a removing liquid for an etching mask is used for a long time, the removability of the etching mask may gradually decrease.

When the removing liquid is used for a long time, although the details are not clear, it is estimated that the removing property is gradually deteriorated due to an increase in carbonate caused by dissolution of carbon dioxide in the air, mixing of components in the positive photosensitive composition layer, and the like.

As a result of extensive and intensive studies, the inventors of the present invention have concluded that, in the method for producing a circuit board according to the present invention, the solubility in a removing liquid and the permeability of the removing liquid are improved by blanket exposure of the positive photosensitive composition layer used as an etching mask after the etching step, and the removing liquid is excellent even when the removing liquid is used for a long period of time.

Further, it was found that the etching mask removal performance is further excellent when the removing liquid is used for a long time by including a step (heating step) of heating the blanket-exposed positive photosensitive composition layer between the step of blanket-exposing the positive photosensitive composition layer and the step of removing the blanket-exposed positive photosensitive composition layer. It is presumed that the reaction due to exposure in the positive photosensitive composition layer can be accelerated by including the heating step, and the reaction is accelerated even in the vicinity of the conductive layer substrate where the reaction is likely to be suppressed due to insufficient exposure, and the solubility to the removing solution and the permeability of the removing solution are improved, and the removing property of the etching mask is further excellent.

Further, it is estimated that when the removing solution is used for a long time, a base (inorganic base or organic base) in the removing solution reacts with carbon dioxide dissolved from the air to form carbonate, and the salt concentration in the removing solution increases with time.

It is concluded that: in order to dissolve the polymer contained in the positive photosensitive composition layer (etching mask) with the removing solution, it is necessary to diffuse the polymer into the aqueous solution by charge repulsion (repulsion) between the polymers in the removing solution, but if the salt concentration in the removing solution is increased, the thickness of the electric double layer in the polymer surface is reduced, the repulsion between the polymers is reduced, and thus the polymer cannot diffuse sufficiently, and the removability is reduced.

It is concluded that: the solubility of the positive resin composition layer is improved by blanket exposure before removal, and particularly, the acid value of the polymer is increased by generating an acid group by decomposition of an acid-decomposable group, so that the repulsive force acting between the polymers can be increased, and the removability is further excellent even when the removing liquid is used for a long time.

In addition, 2 preferable embodiments are described below as a method of manufacturing a circuit board according to the present invention.

Embodiment 1 of the method for manufacturing a circuit board sequentially includes:

a step (forming step) of forming a positive photosensitive composition layer on a conductive layer in a substrate;

a step (exposure step) of pattern-exposing the positive photosensitive composition layer;

a step (developing step) of developing the pattern-exposed positive photosensitive composition layer;

a step (etching step) of etching the conductive layer using the developed positive photosensitive composition layer as a mask;

a step of blanket-exposing the developed positive photosensitive composition layer (blanket exposure step); and

and a step (removal step) of removing the blanket-exposed positive photosensitive composition layer.

The substrate in embodiment 1 of the method for manufacturing a circuit board may be a substrate itself such as glass, silica, or a film, or a substrate in which an arbitrary layer such as a conductive layer is provided on a substrate such as glass, silica, or a film as necessary.

According to embodiment 1 of the method for manufacturing a circuit board, a fine pattern can be formed on the surface of a substrate.

Embodiment 2 of the method for manufacturing a circuit board sequentially includes:

a step of forming a positive photosensitive composition layer on a substrate which has a substrate and a plurality of conductive layers including a1 st conductive layer and a2 nd conductive layer which are different in constituent material from each other, and on which the 1 st conductive layer and the 2 nd conductive layer, which are the outermost layers, are laminated in this order from the far side to the near side of the surface of the substrate;

a1 st exposure step of pattern-exposing the positive photosensitive composition layer;

a1 st developing step of developing the pattern-exposed positive photosensitive composition layer to form a1 st pattern;

a1 st etching step of etching at least the 1 st conductive layer and the 2 nd conductive layer in the plurality of conductive layers in a region where the 1 st pattern is not arranged;

a2 nd exposure step of pattern-exposing the 1 st pattern after the 1 st etching step with a pattern different from the 1 st pattern;

a2 nd developing step of forming a2 nd pattern by developing the 1 st pattern after the 2 nd exposure step;

a2 nd etching step of etching at least the 1 st conductive layer among the plurality of conductive layers in a region where the 2 nd pattern is not arranged;

a step of performing blanket exposure on the 2 nd pattern; and

and removing the 2 nd pattern.

As embodiment 2, international publication No. 2006/190405 can be referred to, and the contents thereof are incorporated in the present specification.

Further, the circuit board can be manufactured by repeatedly applying the method for manufacturing a circuit board according to embodiment 1 to a substrate having a base material and a plurality of conductive layers including the 1 st conductive layer and the 2 nd conductive layer which are different in constituent material from each other.

Hereinafter, a method for manufacturing a circuit board according to the present invention will be described in detail.

< Forming Process >

The method for manufacturing a circuit board according to the present invention includes a step (forming step) of forming a positive photosensitive composition layer (also simply referred to as "photosensitive composition layer") on a conductive layer.

The method of forming the positive photosensitive composition layer on the conductive layer is not particularly limited, and known methods can be used, and examples thereof include a method of forming a positive photosensitive composition layer on the conductive layer by coating, a method of forming a positive photosensitive composition layer on the conductive layer by transferring a positive photosensitive composition layer using a photosensitive transfer material, and the like.

The coating method is not particularly limited, and coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.

Among them, from the viewpoint of simplicity and reduction in the number of steps, a method of forming a positive photosensitive composition layer on a conductive layer by transferring the positive photosensitive composition layer using a photosensitive transfer material is preferably given.

The photosensitive transfer material is preferably a material having a photosensitive composition layer on a temporary support.

The outermost layer on the photosensitive composition layer side may be a photosensitive composition layer based on the temporary support, or may be another layer formed on the photosensitive composition layer.

The details of the positive photosensitive composition layer of the present invention and the photosensitive transfer material used in the present invention will be described later.

Fig. 1 (a) schematically shows an example of a step of forming a positive photosensitive composition layer in the case where the positive photosensitive composition layer is formed on the conductive layer.

First, in the bonding step, the photosensitive composition layer 12 of the photosensitive transfer material 100 according to the present invention is bonded by contacting the 1 st conductive layer 24 and the 2 nd conductive layer 24 with each other, in a bonding step, to a substrate (circuit-wiring-forming substrate) 20 which has a base 22 and a plurality of conductive layers including the 1 st conductive layer 24 and the 2 nd conductive layer 26 having different constituent materials, and in which the 1 st conductive layer 24 and the 2 nd conductive layer 26, which are the outermost layers, are laminated in this order from the far side to the near side of the surface of the base 22 on the surface of the base 22. The bonding of such a circuit wiring forming substrate and a photosensitive transfer material is sometimes referred to as "transfer" or "lamination".

In addition, the photosensitive composition layer using the transfer material can be formed by transferring the photosensitive composition layer from a substrate on which a pattern of the conductive layer is formed.

As shown in fig. 2, in the case where the cover film 16 is provided on the photosensitive composition layer 12 of the photosensitive transfer material 100, after the cover film 16 is removed from the photosensitive transfer material 100 (photosensitive composition layer 12), the photosensitive composition layer 12 of the photosensitive transfer material 100 is brought into contact with the 1 st conductive layer 24 and bonded thereto.

The photosensitive transfer material is preferably applied (transferred) to the 1 st conductive layer by superposing the photosensitive composition layer side of the photosensitive transfer material on the 1 st conductive layer and applying pressure and heat by a roller or the like. For bonding, a known laminator such as a laminator, a vacuum laminator, and an automatic-cutting laminator (Auto-Cutlaminator) capable of further improving productivity can be used.

When the base material of the circuit wiring forming substrate is a resin film, the circuit wiring forming substrate can be attached to the base material in a roll-to-roll manner.

[ substrate ]

The conductive layer is preferably provided on a substrate.

In the substrate in which a plurality of conductive layers are laminated on a base material, the base material is preferably a glass base material or a film base material, more preferably a film base material, and still more preferably a resin film. In the method for manufacturing a circuit board according to the present invention, the base material is preferably a sheet-like resin composition in particular in the case of a circuit board for a touch panel.

Also, the substrate is preferably transparent.

The refractive index of the base material is preferably 1.50 to 1.52.

The substrate may be a light-transmitting substrate such as a Glass substrate, and a strengthened Glass represented by Gorilla Glass (Gorilla Glass) of Corning Incorporated co. As the transparent substrate, materials used in japanese patent application laid-open nos. 2010-086684, 2010-152809, and 2010-257492 can be preferably used.

When a film substrate is used as the substrate, a substrate having a small optical strain and a substrate having a high transparency are more preferably used, and a resin film is more preferably used.

[ conductive layer ]

As the plurality of conductive layers formed on the substrate, any conductive layer used for a general circuit wiring or touch panel wiring can be given.

The conductive layer is preferably at least 1 layer selected from the group consisting of a metal layer and a conductive metal oxide layer, more preferably a metal layer, and particularly preferably a copper layer, from the viewpoint of conductivity and thin line formability.

The substrate may have 1 conductive layer or 2 or more conductive layers. When the number of layers is 2 or more, it is preferable to have conductive layers of different materials.

Examples of the material of the conductive layer include a metal and a conductive metal oxide.

Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.

Examples of the conductive metal Oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO (silicon Oxide)₂And the like. In the present invention, "conductive" means that the volume resistivity is less than 1 × 10⁶Omega cm, preferably having a volume resistivity of less than 1X 10⁴Ωcm。

In the method for manufacturing a circuit board according to the present invention, it is preferable that at least one of the plurality of conductive layers contains a conductive metal oxide.

The conductive layer is preferably an electrode pattern or a wiring of an edge lead portion of a sensor corresponding to a viewing portion used in the electrostatic capacitance type touch panel.

[ substrate for forming circuit Wiring ]

Is a substrate having a conductive layer on the surface of a base material. The circuit wiring is formed by patterning the conductive layer. In the present invention, a substrate in which a plurality of conductive layers of a conductive metal oxide, a metal, or the like are provided on a resin film of PET or the like is preferable.

< Exposure Process (1 st Exposure Process) >

The method for manufacturing a circuit board according to the present invention includes a step of pattern-exposing the positive photosensitive composition layer (exposure step).

The exposure step is performed in embodiment 1, and the exposure step 1 is performed in embodiment 2. An example of the exposure step (1 st exposure step) is schematically shown in fig. 1 (b).

In the exposure step (1 st exposure step), the photosensitive composition layer 12 is pattern-exposed through the temporary support 10 of the photosensitive transfer material after the bonding step.

As examples of the exposure step, the development step, and other steps in the present invention, the methods described in paragraphs 0035 to 0051 of japanese patent application laid-open No. 2006-023696 can also be preferably used in the present invention.

For example, a method in which a mask 30 having a predetermined pattern is disposed above the photosensitive transfer material 100 disposed on the 1 st conductive layer 24 (on the side opposite to the side in contact with the 1 st conductive layer 24), and then, exposure is performed with ultraviolet light from above the mask through the mask 30, and the like can be given.

The detailed arrangement and specific dimensions of the pattern in the present invention are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) including an input device having circuit wirings manufactured by the method for manufacturing a circuit substrate according to the present invention and to reduce the area occupied by lead-out wirings as much as possible, at least a part of the pattern (particularly, an electrode pattern of the touch panel and a part of the lead-out wirings) is preferably a thin line of 100 μm or less, and more preferably a thin line of 70 μm or less.

The light source used for the exposure can be appropriately selected and used as long as it can irradiate light (for example, 365nm, 405nm or the like) in a wavelength region in which the exposed portion of the photosensitive composition layer can be dissolved in the developer. Specifically, an ultra-high pressure mercury lamp, a metal halide lamp, and the like can be given.

The exposure amount is preferably 5mJ/cm²～200mJ/cm²More preferably 10mJ/cm²～100mJ/cm²。

In addition, the pattern exposure in the case of using the photosensitive transfer material may be performed after the temporary support is peeled from the photosensitive composition layer, or may be performed via the temporary support before the temporary support is peeled, and then the temporary support is peeled. In order to prevent contamination of the mask due to contact between the photosensitive composition layer and the mask and to avoid the influence of foreign matter adhering to the mask on the exposure, it is preferable to perform exposure without peeling the temporary support. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

< developing step (1 st developing step) >)

The method for manufacturing a circuit board according to the present invention includes a step of developing the positive photosensitive composition layer subjected to pattern exposure (developing step).

The developing step is performed in embodiment 1, and the developing step 1 is performed in embodiment 2. An example of the developing step (1 st developing step) is schematically shown in fig. 1 (c).

In the developing step (1 st developing step), after the temporary support 10 is peeled off from the photosensitive composition layer 12 after the exposure step (1 st exposure step), the photosensitive composition layer 12 after the exposure step (1 st exposure step) is developed to form the 1 st pattern 14A.

The developing step (1 st developing step) is a step of forming a pattern (1 st pattern) by developing the photosensitive composition layer exposed by the pattern.

The development of the pattern-exposed photosensitive composition layer can be performed using a developer.

The developing solution is not particularly limited as long as the exposed portion of the photosensitive composition layer can be removed, and a known developing solution such as that described in japanese patent application laid-open No. 5-072724 can be used. The developing solution is preferably a developing solution for subjecting the exposed portion of the photosensitive composition layer to dissolution-type development. For example, the developer is preferably an aqueous alkaline developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05mol/L (liter) to 5 mol/L. The developer may further contain an organic solvent miscible with water, a surfactant, and the like. As the developer preferably used in the present invention, for example, the developer described in paragraph 0194 of international publication No. 2015/093271 can be cited.

The developing method is not particularly limited, and may be any of spin-on immersion development, shower and spin development, immersion development, and the like. In the case of the shower development, the exposed portion can be removed by spraying a developer solution onto the exposed photosensitive composition layer. After development, it is preferable to remove the development residue by spraying a cleaning agent or the like and wiping it with a brush or the like. The liquid temperature of the developing solution is preferably 20 to 40 ℃.

Further, a post-baking step of heat-treating a pattern including the photosensitive composition layer obtained by development may be further included.

The post-baking is preferably heated in an environment of 8.1kPa to 121.6kPa, and more preferably in an environment of 506.6kPa or higher. On the other hand, it is more preferably carried out under an environment of 1114.6kPa or less, and particularly preferably carried out under an environment of 101.3kPa or less.

The temperature of the postbaking is preferably from 80 ℃ to 250 ℃, more preferably from 110 ℃ to 170 ℃, and particularly preferably from 130 ℃ to 150 ℃.

The post-drying time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.

The post-drying can be carried out in an air environment or a nitrogen replacement environment.

Other steps such as a post-exposure step may be provided before the etching step.

< etching step (1 st etching step) >)

The method for manufacturing a circuit board according to the present invention includes a step of etching the conductive layer using the developed positive photosensitive composition layer as a mask (etching step).

The etching step is performed in embodiment 1, and the etching step 1 is performed in embodiment 2. An example of the etching step (1 st etching step) is schematically shown in fig. 1 (d).

In the etching step (1 st etching step), at least the 1 st conductive layer 24 and the 2 nd conductive layer 26 are etched in the plurality of conductive layers in the region where the 1 st pattern 14A is not arranged. By etching, the 1 st conductive layer 24A and the 2 nd conductive layer 26A having the same pattern are formed.

The conductive layer can be etched by a known method such as the method described in paragraphs 0048 to 0054 of jp 2010-152155 a or the method based on dry etching such as known plasma etching.

For example, the etching method may be a wet etching method in which the substrate is immersed in an etching solution, which is generally performed. The etching solution used in the wet etching may be an acidic type or an alkaline type, as appropriate, depending on the etching target.

Examples of the acidic etching solution include an aqueous solution of a single acidic component such as hydrochloric acid, sulfuric acid, hydrofluoric acid, or phosphoric acid, and a mixed aqueous solution of an acidic component and a salt such as ferric chloride, ammonium fluoride, or potassium permanganate. The acidic component may be a component in which a plurality of acidic components are combined.

Examples of the alkaline type etching solution include an aqueous solution of a single alkali component such as a salt of an organic amine such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, or tetramethylammonium hydroxide, and a mixed aqueous solution of an alkali component and a salt such as potassium permanganate. The alkali component may be a combination of a plurality of alkali components.

The temperature of the etching solution is not particularly limited, but is preferably 45 ℃ or lower. In the present invention, the 1 st pattern used as an etching mask (etching pattern) preferably exhibits particularly excellent resistance to an acidic and alkaline etching solution in a temperature range of 45 ℃. Therefore, the photosensitive composition layer can be prevented from being peeled off in the etching step, and a portion where the photosensitive composition layer is not present can be selectively etched.

After the etching step, a cleaning step and a drying step may be performed as necessary in order to prevent contamination of the production line.

As the cleaning liquid used in the cleaning step, pure water or an aqueous solution in which an organic solvent or a surfactant that is soluble in pure water is mixed can be used. From the viewpoint of suppressing peeling unevenness caused by droplets remaining on the substrate surface and improving the removal performance, the cleaning liquid is preferably an aqueous solution in which an organic solvent or a surfactant that can be dissolved in pure water is mixed, and more preferably an aqueous solution in which both an organic solvent and a surfactant that can be dissolved in pure water are mixed.

The water-soluble organic solvent to be mixed with water is not particularly limited, but from the viewpoint of the volatility of the solvent, a solvent having a boiling point of 50 to 250 ℃ is preferable, a solvent having a boiling point of 55 to 200 ℃ is more preferable, and a solvent having a boiling point of 60 to 150 ℃ is even more preferable.

Examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol and ethylene glycol, alkoxyalcohols such as 2-acetoxy-2-phenylethyl alcohol, 3-methoxy-3-methyl ethanol, 3-methoxy-3-methyl butanol and 2-butoxyethoxyethanol, ketones such as acetone and methyl ethyl ketone, glycol ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether, tetrahydrofuran, acetonitrile, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide and 1, 3-dioxolane.

Among them, preferred are methanol, ethanol, propanol, isopropanol, 3-methoxy-3-methylbutanol, 2-acetoxy-2-phenylethyl alcohol, tetrahydrofuran, and dimethyl sulfoxide.

The content of the water-soluble organic solvent mixed with water is preferably 0.01 to 95% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.01 to 10% by mass, and particularly preferably 0.01 to 5% by mass, based on the total mass of the aqueous solution.

The surfactant to be mixed with water is not particularly limited as long as it is a water-soluble surfactant, and any of anionic, cationic, Nonionic (Nonionic), and amphoteric surfactants can be used. From the viewpoint of suppressing foaming of the cleaning liquid, a nonionic surfactant is preferable.

Examples of the anionic surfactant include carboxylates, sulfonates, sulfates, and phosphates.

Examples of the cationic surfactant include amine salts and quaternary ammonium salts.

Examples of the amphoteric surfactant include betaine type surfactants.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, alkylbenzene polyalkylene glycols, polyoxyalkylene glycols, silicone surfactants, and fluorine surfactants.

Further, the following series of trade names can be cited: KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), EFTOP (JAPAN Electronic MONETARY CLAIMORGANIZATION), Megaface (CORDIC PORATION), Fluorad (Sumitomo 3M Limited), Asahiguard, Surflow (Asahi Glass Co., Ltd.), PolyFox (OMNOVA SOLUTION INC.), Surfinol (Nissin Chemical co., Ltd.), and Cor-8400 (Dow coming Toray Co., Ltd.), and the like.

The surfactant may be used alone in 1 kind, or may be used in 2 or more kinds at the same time, and preferably in 2 or more kinds at the same time.

The content of the surfactant to be mixed with water is preferably 10% by mass or less, more preferably 0.001% by mass to 5% by mass, and still more preferably 0.01% by mass to 3% by mass, based on the total mass of the aqueous solution.

The surface tension of the aqueous solution mixed with the water-soluble organic solvent or the surfactant is preferably 50mN/m or less, more preferably 10mN/m to 50mN/m, even more preferably 15mN/m to 40mN/m, and most preferably 20mN/m to 40mN/m, from the viewpoint of suppressing peeling unevenness caused by droplets remaining on the substrate surface and improving the removability.

The cleaning time in the cleaning step is not particularly limited, but is preferably 10 to 300 seconds, for example, for cleaning the substrate, and the drying step is preferably performed by using a blower, for example, and appropriately adjusting the blower pressure (preferably 0.1 kg/cm)²～5kg/cm²Left and right) to be dried.

< 2 nd Exposure Process >

In embodiment 2, the 2 nd exposure step is performed. An example of the 2 nd exposure step is schematically shown in fig. 1 (e).

After the 1 st etching step, the 1 st pattern 14A after the 1 st etching step is pattern-exposed in a pattern different from the 1 st pattern.

In the 2 nd exposure step, a portion corresponding to at least a portion to be removed of the 1 st conductive layer in the 2 nd development step described later is exposed to the 1 st pattern remaining on the 1 st conductive layer.

The same method as the pattern exposure in the 1 st exposure step can be applied except that the mask 40 having a pattern different from that of the mask 30 used in the 1 st exposure step is used in the pattern exposure in the 2 nd exposure step.

< 2 nd developing step >

The 2 nd developing step is performed in embodiment 2. An example of the 2 nd developing step is schematically shown in fig. 1 (f).

In the 2 nd developing step, the 1 st pattern 14A after the 2 nd exposure step is developed to form a2 nd pattern 14B.

By the development, the portion of the 1 st pattern exposed in the 2 nd exposure step is removed.

In the 2 nd developing step, the same method as that used in the 1 st developing step can be applied.

< 2 nd etching Process >

In embodiment 2, the 2 nd etching step is performed. An example of the 2 nd etching step is schematically shown in fig. 1 (g).

In the 2 nd etching step, at least the 1 st conductive layer 24A is etched in the plurality of conductive layers in the region where the 2 nd pattern 14B is not arranged.

The same method as that used in the etching in the first etching step 1 can be applied except that an etching solution corresponding to the conductive layer to be removed by etching is selected in the etching in the second etching step 2.

In the second etching step, it is preferable that the conductive layer is selectively etched less than in the first etching step in accordance with a desired pattern. For example, as shown in fig. 1, the pattern of the 1 st conductive layer can be made different from the pattern of the 2 nd conductive layer by performing etching using an etching solution that selectively etches only the 1 st conductive layer 24B in a region where the photosensitive composition layer is not disposed.

After the 2 nd etching step is completed, circuit wirings including at least 2 kinds of patterned

conductive layers

24B and 26A are formed.

< Overall Exposure Process >

The method for manufacturing a circuit board according to the present invention includes, after the etching step and before the removing step, a step of blanket-exposing the developed positive photosensitive composition layer (blanket-exposing step).

In the present invention, the term "exposing the entire surface of the developed positive photosensitive composition layer" means exposing the entire positive photosensitive composition layer which remains after development, and the portion without the positive photosensitive composition layer may be exposed or not exposed.

The light source used for the exposure in the blanket exposure step is not particularly limited, and a known exposure light source can be used. Specifically, an ultra-high pressure mercury lamp, a metal halide lamp, a Light Emitting Diode (LED), and the like can be given.

In the blanket exposure step, it is preferable to use a light source containing light having the same wavelength as that in the exposure step from the viewpoint of removability.

The exposure amount in the blanket exposure step is preferably 5mJ/cm from the viewpoint of removability²～1,000mJ/cm²More preferably 10mJ/cm²～800mJ/cm²Particularly preferably 100mJ/cm²～500mJ/cm²。

Further, the exposure amount in the blanket exposure step is preferably not less than the exposure amount in the exposure step, and more preferably more than the exposure amount in the exposure step, from the viewpoint of removability.

Further, the exposure illuminance in the blanket exposure step is preferably 5mW/cm²～25,000mW/cm²More preferably 20mW/cm²～20,000mW/cm²Particularly preferably 30mW/cm²～15,000mW/cm². In fact, the time required for blanket exposure is shortened by setting the illuminance high, and hence the time required for the process is reducedFrom the viewpoint of this, the most appropriate exposure illuminance can be selected.

In addition, the step of heating the substrate may be included before the blanket exposure, during the blanket exposure, or both, from the viewpoint of increasing the reaction rate of the photoacid generator and the viewpoint of removing excess moisture. The heating device is not particularly limited, and a known heating device can be used. Specifically, an IR (Infrared Ray) heater, a warm air drying machine, a hot air blower, a flow oven, or the like can be used.

The heating temperature in the step of heating the substrate before the blanket exposure, during the blanket exposure, or both is preferably 30 to 100 ℃, and more preferably 30 to 60 ℃.

The time for heating in the step of heating the substrate before the blanket exposure, during the blanket exposure, or both of them can be appropriately selected in consideration of the time required in the blanket exposure step, and the like, but heating is preferably performed for 1 to 600 seconds, and particularly preferably for 5 to 60 seconds.

In the method for manufacturing a circuit board according to the present invention, it is preferable that the method for manufacturing a circuit board does not include a step of etching the conductive layer using the developed positive photosensitive composition layer as a mask after the blanket exposure step.

< heating Process >

The method for manufacturing a circuit board according to the present invention may further include a step (heating step) of heating the blanket-exposed positive photosensitive composition layer during the blanket exposure step, after the exposure step, or both of them and before the removal step described later. By including the heating step, the reaction rate of the photoacid generator and the reaction rate of the generated acid with the positive photosensitive composition can be further increased, and as a result, the removal performance can be improved.

The heating device used in the heating step is not particularly limited, and a known heating device can be used. Specifically, an IR heater, warm air drying, hot air blower, flow oven, or the like can be used.

The heating temperature in the heating step is preferably 30 to 100 ℃, more preferably 30 to 80 ℃, and particularly preferably 30 to 60 ℃ from the viewpoint of removability.

The heating time in the heating step is preferably 1 to 600 seconds, more preferably 1 to 120 seconds, and particularly preferably 5 to 60 seconds, from the viewpoint of removability. The heating time in the present invention is a time after the substrate reaches the set temperature, and does not include a time during the temperature rise.

The atmosphere in the heating step is preferably atmospheric air (the relative humidity is 10% RH to 90% RH), but heating may be performed in an atmosphere purged with an inert gas such as nitrogen or argon as necessary, such as deoxidation.

In addition, when a large amount of water adheres to the substrate, a step of blowing off excess water with an air knife or the like may be combined before, during, or both the heating step from the viewpoint of improving the heating efficiency.

< removal Process >

The method for manufacturing a circuit board according to the present invention includes a step (removal step) of removing the blanket-exposed positive photosensitive composition layer. The removal in the removal step includes, for example, dissolution and dispersion of the removal liquid in the positive photosensitive composition layer.

An example of the removal step is schematically shown in fig. 1 (h).

After the 2 nd etching step is completed, the 2 nd pattern 14B remains on a part of the 1 st conductive layer 24B. All the remaining photosensitive composition layer, i.e., the 2 nd pattern 14B, is removed.

The method for removing the residual photosensitive composition layer is not particularly limited, but a method for removing by a chemical treatment can be mentioned, and a removing liquid can be particularly preferably used.

The method for removing the photosensitive composition layer includes a method in which a substrate having the photosensitive composition layer or the like is immersed in a removing solution while stirring, preferably at 30 to 80 ℃, more preferably at 50 to 80 ℃ for 1 to 30 minutes.

In the removal step, from the viewpoint of removability, a removal liquid containing 30% by mass or more of water is preferably used, more preferably 50% by mass or more of water is used, and still more preferably 70% by mass or more of water is used.

The removal liquid is preferably a removal liquid containing an inorganic base component such as sodium hydroxide or potassium hydroxide, or an organic base component such as a primary amine compound, a secondary amine compound, a tertiary amine compound, or a quaternary ammonium salt compound.

Among these, from the viewpoint of removability, a removal liquid containing an organic base component is more preferable, and an amine compound is particularly preferable.

The content of the alkali component may be appropriately selected from the viewpoint of the alkali strength, solubility, and the like, but from the viewpoint of removability, the content is preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass, based on the total mass of the removal liquid.

From the viewpoint of removability, the removing solution preferably contains a surfactant.

As the surfactant, a known surfactant can be used.

From the viewpoint of removability, the content of the surfactant is preferably 0.1 to 10% by mass relative to the total mass of the removal liquid.

Further, it is preferable that the removing solution contains a water-soluble organic solvent.

Preferable examples of the water-soluble organic solvent include dimethyl sulfoxide and N-methylpyrrolidone.

In the above-mentioned removing step, a method of removing the metal oxide by a spray method, a shower method, a spin-coating immersion method, or the like using a removing liquid is preferably exemplified.

< volume to volume approach >

The method of manufacturing a circuit board according to the present invention is preferably performed by a roll-to-roll method.

The roll-to-roll method is a method in which: a substrate that can be wound and unwound is used as the substrate, and the method includes an unwinding step of unwinding the substrate or the structure formed in the forming step before any one of the steps included in the method for manufacturing the circuit substrate, and a winding step of winding the substrate or the structure after any one of the steps, and performs at least any one of the steps (preferably all of the steps or all of the steps except the heating step) while conveying the substrate or the structure.

The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and any known method in the roll-to-roll manufacturing method may be used.

Specifically, it is preferable that the method further includes a step of winding a structure in which the photosensitive composition layer formed in the forming step is bonded to the substrate and a step of unwinding the structure between the forming step, the exposure step (first exposure step or second exposure step), the heating step (first heating step or second heating step), the development step (first development step or second development step), the etching step (first etching step or second etching step), the blanket exposure step, and the removal step.

Preferably, the method further includes, before the forming step, a step of unwinding a roll substrate prepared by preparing and winding a conductive layer such as a metal on a film such as a resin film, and forming the photosensitive composition layer on the conductive layer in the unwound roll substrate.

The method of manufacturing a circuit board according to the present invention may further include any other steps. For example, the following steps are included, but the present invention is not limited to these steps.

< Process of attaching protective film >

In embodiment 2, a step of attaching a light-transmitting protective film (not shown) to the 1 st pattern may be provided after the 1 st etching step and before the 2 nd exposure step.

In this case, it is preferable that the pattern exposure for the 1 st pattern is performed through the protective film in the 2 nd exposure step, and after the 2 nd exposure step, the protective film is removed from the 1 st pattern, and then the 2 nd development step is performed.

< Process for reducing reflectance of visible ray >

The method for manufacturing a circuit board according to the present invention may include a step of performing a treatment for reducing the visible light reflectance of a part or all of the plurality of conductive layers on the base material.

Examples of the treatment for reducing the visible light reflectance include oxidation treatment. For example, the visible light reflectance can be reduced by performing an oxidation treatment on copper to form copper oxide and blackening the copper oxide.

Preferable modes of the treatment for reducing the reflectance of visible light are described in paragraphs 0017 to 0025 of Japanese patent laid-open No. 2014-150118 and paragraphs 0041, 0042, 0048 and 0058 of Japanese patent laid-open No. 2013-206315, and the contents of these publications are incorporated in the present specification.

< Process for Forming New conductive layer on insulating film >

The method of manufacturing a circuit board according to the present invention preferably includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film.

With this configuration, the second electrode pattern can be formed so as to be insulated from the first electrode pattern.

The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be mentioned. Further, an insulating film having a desired pattern may be formed by photolithography using an insulating photosensitive material.

The step of forming a new conductive layer on the insulating film is not particularly limited. A new conductive layer of a desired pattern can be formed by photolithography using a photosensitive material having conductivity.

Further, although the description of fig. 1 has been given of the case where the circuit wiring having 2 different patterns is formed on the circuit wiring forming substrate having 2 conductive layers, the number of conductive layers of the substrate to which the method for manufacturing a circuit substrate according to the present invention is applied is not limited to 2, and 3 or more conductive layers can be formed into different circuit wiring patterns by performing 3 or more combinations of the above-described exposure step, development step, and etching step using a circuit wiring forming substrate on which 3 or more conductive layers are stacked.

Further, although not shown in fig. 1, in the method for manufacturing a circuit board according to the present invention, it is also preferable that the base has a plurality of conductive layers on both surfaces thereof, and that a circuit is formed in the conductive layers formed on both surfaces of the base sequentially or simultaneously. With this configuration, a circuit board for a touch panel can be formed in which the first conductive pattern is formed on one surface of the base material and the second conductive pattern is formed on the other surface. Further, it is also preferable that the circuit board for a touch panel having such a configuration is formed from both surfaces of the base material in a roll-to-roll manner.

< Positive photosensitive composition layer >

The positive photosensitive composition layer used in the present invention is not particularly limited, and a known positive photosensitive composition layer can be used. In addition, from the viewpoint of sensitivity, resolution, and removability, the photosensitive composition layer is preferably a chemically amplified positive photosensitive composition layer containing a polymer containing a constituent unit having an acid group protected by an acid-decomposable group and a photoacid generator.

In the photoacid generator such as an onium salt or an oxime sulfonate compound described later, since an acid generated by the induction of active radiation (active light) acts as a catalyst for the deprotection of a protected acid group in the polymer, the acid generated by the action of 1 photon contributes to a large number of deprotection reactions, and the quantum yield exceeds 1 to a value as large as, for example, a power of 10, and as a result of so-called chemical amplification, high sensitivity is obtained.

On the other hand, when a quinonediazide compound is used as a photoacid generator for sensitive active radiation, a carboxyl group is generated by a sequential photochemical reaction, but the quantum yield is always 1 or less, and a chemical amplification type is not satisfied.

[ Polymer A1 containing a Polymer having a constitutional Unit having an acid group protected by acid decomposability ]

The photosensitive composition layer preferably includes a polymer (also simply referred to as "polymer a 1") containing a constituent unit (also referred to as "constituent unit a") having an acid group protected by acid decomposability.

The photosensitive composition layer may contain other polymers in addition to the polymer a1 containing the constituent unit a. In the present invention, the polymer a1 containing the constituent unit a and other polymers are also collectively referred to as "polymer components".

The polymer component does not contain a surfactant described later.

Therefore, in the case where the photosensitive composition layer does not contain a resin component other than the polymer component and the surfactant, the resin component in the photosensitive composition layer refers to the polymer component.

The polymer a1 described above is such that the constitutional unit a having an acid group protected with an acid-decomposable group in the polymer a1 is subjected to deprotection reaction by the action of a catalytic amount of an acidic substance generated by exposure to light, and becomes an acid group. The acid group can be dissolved in the developer.

Further, the polymer a1 preferably further contains a constituent unit having an acid group.

The polymer a1 is preferably a non-particulate polymer (also referred to as a "binder polymer") from the viewpoint of pattern shape, solubility in a developer, and transferability.

Preferred embodiments of the constituent unit a will be described below.

The photosensitive composition layer may further include a polymer other than the polymer a1 containing a constituent unit having an acid group protected by an acid-decomposable group.

Further, all the polymers contained in the polymer component are preferably polymers each containing at least a constituent unit having an acid group described later.

The photosensitive composition may contain a polymer other than these. Unless otherwise specified, the polymer component in the present invention means that other polymers are contained as needed. Further, even if the compound conforming to the crosslinking agent and the dispersing agent described later is a polymer compound, it is not included in the polymer component.

The polymer a1 is preferably an addition polymerization type resin, and more preferably a polymer having a constituent unit derived from (meth) acrylic acid or an ester thereof. In addition, the resin composition may have a constituent unit other than the constituent unit derived from (meth) acrylic acid or an ester thereof, for example, a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or the like.

From the viewpoint of suppressing deformation of the pattern shape, solubility in a developer, and transferability, the photosensitive composition layer preferably contains, as the polymer component, a polymer having at least 1 type of constituent unit selected from the group consisting of the constituent units represented by any of the formulae a1 to A3 as the constituent unit a, and more preferably contains, as the polymer component, a polymer having at least 1 type of constituent unit selected from the group consisting of the constituent units represented by any of the formulae a1 to A3 and an acid group as the constituent unit a.

The number of the polymers a1 included in the photosensitive composition layer may be only 1, or may be 2 or more.

The constituent unit A-

The polymer component is preferably a polymer a1 containing at least a constituent unit a having an acid group protected by an acid-decomposable group. By including the polymer containing the constituent unit a in the polymer component, a chemically amplified positive photosensitive composition layer with extremely high sensitivity can be obtained.

In the "acid group protected with an acid-decomposable group" in the present invention, a known acid group and acid-decomposable group can be used as the acid group and acid-decomposable group, and there is no particular limitation. Specific examples of the acid group include a carboxyl group and a phenolic hydroxyl group. As the acid group protected by the acid-decomposable property, a group which is relatively easily decomposed by an acid (for example, an ester group protected by a group represented by formula a3, an acetal functional group such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group) or a group which is relatively easily decomposed by an acid (for example, a tertiary alkyl group such as a tertiary butyl ester group or a tertiary alkyl carbonate group such as a tertiary butyl carbonate group) can be used.

Among these, the acid-decomposable group is preferably a group having a structure protected in the form of acetal.

The acid-decomposable group is preferably an acid-decomposable group having a molecular weight of 300 or less, from the viewpoint of suppressing variation in line width in the obtained circuit wiring.

From the viewpoint of sensitivity and resolution, the constituent unit a having an acid group protected with the acid-decomposable group is preferably at least 1 constituent unit selected from the group consisting of constituent units represented by any of the following formulae a1 to A3, and more preferably a constituent unit represented by the following formula A3-2.

[ chemical formula 3]

In the formula A3, R³¹And R³²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R³¹And R³²Is alkyl or aryl, R³³Represents alkyl or aryl, R³¹Or R³²Can be reacted with R³³Linked to form a cyclic ether, R³⁴Represents a hydrogen atom or a methyl group, X⁰Represents a single bond or an arylene group, and Y represents-S-or-O-.

< preferred mode of the constitutional unit represented by the formula A1 >

In the formula A1, in R¹¹Or R¹²When the alkyl group is used, the alkyl group preferably has 1 to 10 carbon atoms. At R¹¹Or R¹²In the case of aryl, phenyl is preferred. R¹¹And R¹²Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula A1, R¹³Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

And, R¹¹～R¹³The alkyl group and the aryl group in (1) may have a substituent.

In the formula A1, R¹¹Or R¹²Can be reacted with R¹³Linked to form a cyclic ether, preferably R¹¹Or R¹²And R¹³Linked to form a cyclic ether. The number of cyclic elements of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.

In the formula A1, X¹A single bond or a 2-valent linking group is preferably a single bond or an alkylene group, -C (═ O) O-, -C (═ O) NRN-, -O-, or a combination of these, and more preferably a single bond. The alkylene group may be linear, branched, or have a cyclic structure or a substituent. The number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 4. At X^Bwhen-C (═ O) O-is contained, it is preferable that the carbon atom contained in-C (═ O) O-is bonded to R^B4The carbon atoms of (b) are directly bonded. At X¹When the compound contains — C (═ O) NRN —, it is preferably — C (═ O) NR^NCarbon atom contained in (A) with R bonded thereto¹⁴The carbon atoms of (b) are directly bonded. R^NRepresents an alkyl group or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a hydrogen atom.

Of the formula A1, preferablyIs selected to contain R¹¹～R¹³Group of (2) and X¹Bonded in para position to each other.

In the formula A1, R¹⁵Represents a substituent, preferably an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.

In the formula A1, n represents an integer of 0 to 4, preferably 0 or 1, more preferably 0.

In the formula A1, R¹⁴Represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of further lowering the Tg of the polymer a 1.

More specifically, R in the formula A1 is relative to the total content of the constituent units A contained in the polymer A1¹⁴The constituent unit that is a hydrogen atom is preferably 20 mass% or more.

In addition, R in the formula A1 in the constituent unit A¹⁴The content (content ratio: mass ratio) of the constituent unit which is a hydrogen atom can be determined according to¹³The intensity ratio of the peak intensities determined by C-nuclear magnetic resonance spectroscopy (NMR) and calculated by a conventional method was confirmed.

Among the constituent elements represented by formula a1, the constituent element represented by formula a1-2 below is more preferable from the viewpoint of suppressing deformation of the pattern shape.

[ chemical formula 4]

In the formula A1-2, R^B4Represents a hydrogen atom or a methyl group, R^B5～R^B11Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R^B12Represents a substituent, and n represents an integer of 0 to 4.

In the formula A1-2, R^B4Preferably a hydrogen atom.

In the formula A1-2, R^B5～R^B11Preferably a hydrogen atom.

In the formula A1-2, R^B12Represents a substituent, preferably an alkyl group or a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 4.

In the formula A1-2, n represents an integer of 0 to 4, preferably 0 or 1, more preferably 0.

As a preferred specific example of the structural unit a1 represented by formula a1, the following structural units can be exemplified. In addition, R^B4Represents a hydrogen atom or a methyl group.

[ chemical formula 5]

< preferred mode of the constitutional unit represented by the formula A2 >

In the formula A2, in R²¹And R²²When the alkyl group is used, the alkyl group preferably has 1 to 10 carbon atoms. At R²¹And R²²In the case of aryl, phenyl is preferred. R¹¹And R¹²Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably at least one of which is a hydrogen atom.

In the above formula A2, R²³Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

R¹¹Or R¹²Can be reacted with R¹³Linked to form a cyclic ether.

In the formula A2, R is preferred²⁴Each independently is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. R²⁴May be further reacted with R²⁴The same groups are substituted.

In formula a2, m is preferably 1 or 2, more preferably 1.

As a preferred specific example of the structural unit a2 represented by formula a2, the following structural units can be exemplified. In addition, R^B4Represents a hydrogen atom or a methyl group.

[ chemical formula 6]

< preferred mode of the constitutional unit represented by the formula A3 >

In the formula A3, in R³¹Or R³²When the alkyl group is used, the alkyl group preferably has 1 to 10 carbon atoms. At R³¹Or R³²In the case of aryl, phenyl is preferred. R³¹And R³²Each of which is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula A3, R³³Represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

And, R³¹～R³³The alkyl group and the aryl group in (1) may have a substituent.

In the formula A3, R³¹Or R³²Can be reacted with R³³Linked to form a cyclic ether, preferably R³¹Or R³²And R³³Linked to form a cyclic ether. The number of cyclic elements of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.

In the formula A3, X⁰Represents a single bond or an arylene group, preferably a single bond. The arylene group may have a substituent.

In the formula A3, Y represents-S-or-O-, and is preferably-O-from the viewpoint of exposure sensitivity.

The constituent unit represented by the above formula a3 is a constituent unit having a carboxyl group protected with an acid-decomposable group. The polymer a1 contains a constitutional unit represented by formula A3, and thus is excellent in sensitivity at the time of pattern formation and further excellent in resolution.

In the formula A3, R³⁴Represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of further lowering the Tg of the polymer a 1.

More specifically, R in formula A3 is relative to the total amount of the constituent unit represented by formula A3 contained in the polymer a1³⁴The constituent unit that is a hydrogen atom is preferably 20 mass% or more.

In addition, R in the formula A1 among the constituent units represented by the formula A3³⁴The content (content ratio: mass ratio) of the constituent unit which is a hydrogen atom can be determined according to¹³The intensity ratio of the peak intensities determined by C-nuclear magnetic resonance spectroscopy (NMR) and calculated by a conventional method was confirmed.

Among the constituent units represented by formula a3, the constituent unit having an acid group protected by acid decomposition is more preferably the constituent unit represented by formula a below, from the viewpoint of further improving exposure sensitivity at the time of pattern formation.

[ chemical formula 7]

In the formula A, R³¹And R³²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R³¹And R³²Is alkyl or aryl, R³³Represents alkyl or aryl, R³¹Or R³²Can be reacted with R³³Linked to form a cyclic ether, R³⁴Represents a hydrogen atom or a methyl group, X⁰Represents a single bond or a 2-valent linking group.

In the formula A, R³¹、R³²、R³³、R³⁴And X⁰Are each as defined for R in the formula A3³¹、R³²、R³³、R³⁴And X⁰Likewise, the preferred mode is the same.

Among the constituent units represented by formula A3, the constituent unit represented by formula A3-3 below is more preferable from the viewpoint of further improving the sensitivity in pattern formation.

[ chemical formula 8]

In the formula A3-3, R³⁴Represents a hydrogen atom or a methyl group, R³⁵～R⁴¹Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula A3-3, R³⁴Preferably a hydrogen atom.

In the formula A3-3, R³⁵～R⁴¹Preferably a hydrogen atom.

As a preferable specific example of the constituent unit having a carboxyl group protected with an acid-decomposable group represented by formula a3, the following constituent unit can be exemplified. In additionOuter, R³⁴Represents a hydrogen atom or a methyl group.

[ chemical formula 9]

The constituent unit a included in the polymer a1 may be 1 type, or 2 or more types.

The content of the constituent unit a in the polymer a1 is preferably 20% by mass or more, more preferably 20% by mass to 90% by mass, and still more preferably 30% by mass to 70% by mass, based on the total mass of the polymer a 1.

The content (content ratio: mass ratio) of the constituent unit A in the polymer A1 can be determined by¹³C-NMR was measured and confirmed by calculating the intensity ratio of peak intensities by a conventional method.

After all the polymer components are decomposed into constituent units (monomer units), the proportion of the constituent unit a is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 30 to 70% by mass, based on the total mass of the polymer components.

-a constituent unit B-

The polymer a1 preferably contains a constituent unit B having an acid group.

The constituent unit B is a constituent unit having an acid group not protected with a protecting group such as an acid-decomposable group, that is, an acid group not having a protecting group. Since the polymer a1 contains the constituent unit B, the sensitivity during pattern formation is good, and the polymer a1 can be easily dissolved in an alkaline developer in a developing step after pattern exposure, thereby shortening the developing time.

The acid group in the present specification means a proton-dissociative group having a pKa of 12 or less. The acid group is generally incorporated in the polymer using a monomer capable of forming an acid group as a constituent unit having an acid group (constituent unit B). From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. Also, the pKa of the acid group is preferably-5 or more.

Examples of the acid group include a carboxyl group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonimide group. Among them, at least 1 kind of acid group selected from the group consisting of a carboxylic acid group and a phenolic hydroxyl group is preferable.

The introduction of the constituent unit having an acid group into the polymer a1 can be performed by copolymerizing a monomer having an acid group or copolymerizing a monomer having an acid anhydride structure and hydrolyzing the acid anhydride.

The constituent unit having an acid group as the constituent unit B is more preferably a constituent unit derived from a styrene compound or a constituent unit derived from a vinyl compound, which is substituted with an acid group, or a constituent unit derived from (meth) acrylic acid. Specifically, examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxystyrene, and the like, examples of the monomer having a phenolic hydroxyl group include p-hydroxystyrene, 4-hydroxyphenylmethacrylate, and the like, and examples of the monomer having an acid anhydride include maleic anhydride, and the like.

The constituent unit B is preferably a constituent unit having a carboxylic acid group or a constituent unit having a phenolic hydroxyl group, from the viewpoint of better sensitivity in pattern formation.

The monomer having an acid group capable of forming the constituent unit B is not limited to the examples described above.

The number of the constituent units B contained in the polymer a1 may be only 1, or may be 2 or more.

The polymer a1 preferably contains 0.1 to 20% by mass of the constituent unit having an acid group (constituent unit B), more preferably 0.5 to 15% by mass, and still more preferably 1 to 10% by mass, based on the total mass of the polymer a 1. Within the above range, the pattern formability is further improved.

The content (content ratio: mass ratio) of the constituent unit B in the polymer A1 can be determined by¹³C-NMR was measured and confirmed by calculating the intensity ratio of peak intensities by a conventional method.

Other constituent units

The polymer a1 may contain other constituent units (hereinafter, sometimes referred to as a constituent unit C) than the constituent unit a and the constituent unit B described above, within a range not impairing the effects of the photosensitive transfer material according to the present invention.

The monomer forming the constituent unit C is not particularly limited, and examples thereof include styrenes, alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, groups having an aliphatic cyclic skeleton, and other unsaturated compounds.

By using the constituent unit C, various properties of the polymer a1 can be adjusted by adjusting at least one of the type and the content. In particular, the Tg of the polymer a1 can be easily adjusted by appropriately using the constituent unit C.

By setting the glass transition temperature to 120 ℃ or lower, the transferability and removability of the positive photosensitive composition layer containing the polymer a1 from the temporary support are maintained at good levels, and the resolution and sensitivity at the time of pattern formation are further improved.

The polymer a1 may contain only 1 type of the constituent unit C, or may contain 2 or more types.

Specific examples of the constituent unit C include those obtained by polymerizing styrene, t-butoxystyrene, methylstyrene, α -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, vinylmethyl benzoate, vinylethyl benzoate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetylacetate mono (meth) acrylate, and the like, and those described in paragraphs 0021 to 0024 of Japanese patent laid-open No. 2004-462623.

The constituent unit C is preferably a constituent unit having an aromatic ring or a constituent unit having an aliphatic ring skeleton from the viewpoint of improving the electrical characteristics of the obtained transfer material, and specific examples of monomers forming these constituent units include styrene, t-butoxystyrene, methylstyrene, α -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.

In addition, the monomer forming the constituent unit C is preferably, for example, an alkyl (meth) acrylate from the viewpoint of adhesiveness. Among these, alkyl (meth) acrylates having an alkyl group having 4 to 12 carbon atoms are more preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.

The content of the constituent unit C is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less, relative to the total mass of the polymer a 1. The lower limit may be 0 mass%, but is preferably 1 mass% or more, and more preferably 5 mass% or more. Within the above range, the resolution and the adhesion are further improved.

From the viewpoint of optimizing the solubility in a developer and the physical properties of the photosensitive composition layer, the polymer a1 preferably includes, as the constituent unit C, a constituent unit containing an ester having an acid group in the constituent unit B.

Among them, the polymer a1 is preferably a polymer containing a constituent unit having a carboxylic acid group as a constituent unit B and a constituent unit C having a carboxylic acid ester group as a copolymerization component, and more preferably a polymer containing a constituent unit B derived from (meth) acrylic acid and a constituent unit (C) derived from cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or n-butyl (meth) acrylate, for example.

Preferred examples of the polymer a1 in the present invention will be described below, but the present invention is not limited to the examples below. In order to obtain preferable physical properties, the ratio of the constituent units in the following exemplary compounds and the weight average molecular weight can be appropriately selected.

[ chemical formula 10]

Average value of the I/O values of the polymer components-

The polymer component used in the present invention preferably has an average I/O value obtained by dividing the inorganic value I by the organic value O based on the organic conceptual diagram, from the viewpoint of removability, of 0.55 to 0.65 inclusive, and more preferably 0.57 to 0.63 inclusive.

The I/O value of the specific polymer used in the present invention may be appropriately set so that the average value of the I/O values is included in the above range, and is preferably 0.55 or more and 0.65 or less, and more preferably 0.57 or more and 0.63 or less.

Regarding the above I/O values, they were shown in an organic conceptual diagram (Haitian, Kyoritsu Shuppan (1984)); KUAMOTTOPHARMACEUTICAL BULLETIN, item 1 to 16 (1954); chemical field, volume 11, No. 10, items 719-725 (1957); FRAGRANCE JOURNAL, No. 34, items 97 to 111 (1979); FRAGRANCE JOURNAL, item 50, item 79 to 82 (1981); etc. are described in detail in the literature. The concept of I/O value is to separate the properties of a compound into organic groups showing covalent bonding and inorganic groups showing ionic bonding, and to position all organic compounds at every 1 point on the rectangular coordinates named organic axis and inorganic axis.

The I/O value in the case where the polymer component contains 2 or more polymers can be considered as follows. For example, when the polymer component contains 3 kinds of polymers (polymer 1 to polymer 3), the I/O value Am of the mixed component can be estimated as follows when the I/O value of polymer 1 is a1, the mass fraction is M1, the I/O value of polymer 2 is a2, the mass fraction is M2, the I/O value of polymer 3 is A3, and the mass fraction is M3.

Am＝A1×M1+A2×M2+A3×M3

In addition, in the polymer component alone containing only 1 kind of polymer, the I/O value of only 1 kind of polymer contained becomes the average value of the I/O value in the polymer component.

Glass transition temperature of polymer a 1: tg-

The glass transition temperature (Tg) of the polymer a1 in the present invention is preferably 90 ℃ or lower, more preferably 20 ℃ or higher and 60 ℃ or lower, and further preferably 30 ℃ or higher and 50 ℃ or lower, from the viewpoint of transferability and from the viewpoint of adjusting the heating temperature in the heating step.

As a method of adjusting Tg of the polymer to the above-described preferable range, Tg of the polymer a1 can be controlled, for example, by FOX formula in accordance with Tg of individual polymers of each constituent unit of the target polymer and a mass ratio of each constituent unit.

With respect to the formula FOX,

when Tg of the polymer alone of the 1 st constituent unit contained in the polymer is Tg1, mass fraction in the copolymer of the 1 st constituent unit is W1, Tg of the polymer alone of the 2 nd constituent unit is Tg2, and mass fraction in the copolymer of the 2 nd constituent unit is W2, Tg0(K) of the copolymer containing the 1 st constituent unit and the 2 nd constituent unit can be estimated according to the following formula.

FOX formula: 1/Tg0 ═ W1/Tg1) + (W2/Tg2)

By using the above formula FOX, a copolymer having a desired Tg can be obtained by adjusting the kind and mass fraction of each constituent unit contained in the copolymer.

Further, the Tg of the polymer can also be adjusted by adjusting the weight average molecular weight of the polymer.

Acid number of Polymer A1-

The acid value of the polymer a1 is preferably 0mgKOH/g or more and 200mgKOH/g or less, and more preferably 5mgKOH/g or more and 100mgKOH/g or less, from the viewpoint of developability and transferability.

The acid value of the polymer in the present invention represents the mass of potassium hydroxide required for neutralizing 1g of the acidic component of the polymer. Specifically, a measurement sample was dissolved in a tetrahydrofuran/water 9/1 mixed solvent, and the obtained solution was subjected to neutralization titration with a 0.1M aqueous sodium hydroxide solution AT 25 ℃ using a potential difference titration apparatus (trade name: AT-510, KYOTO electroinc manual co., ltd. The inflection point of the titration pH curve was used as the titration end point, and the acid value was calculated according to the following formula.

A＝56.11×Vs×0.1×f/w

A: acid value (mgKOH/g)

Vs: amount of 0.1mol/l aqueous sodium hydroxide solution (mL) required for titration

f: titration amount of 0.1mol/l aqueous solution of sodium hydroxide

w: the mass (g) of the sample was measured (conversion of solid content)

Molecular weight of polymer a 1: mw-

The molecular weight of the polymer a1 is preferably 60,000 or less in terms of polystyrene-reduced weight average molecular weight. The weight average molecular weight of the polymer a1 is 60,000 or less, and therefore, the melt viscosity of the photosensitive composition layer is suppressed to be low, and bonding at a low temperature (for example, 130 ℃ or less) can be achieved when the photosensitive composition layer is bonded to the substrate.

The weight average molecular weight of the polymer A1 is preferably 2,000 to 60,000, more preferably 3,000 to 50,000.

The weight average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as the measuring apparatus, and the contents of the apparatuses and the measuring techniques are well known to those skilled in the art.

In the measurement of the weight average molecular weight by Gel Permeation Chromatography (GPC), HLC (registered trademark) -8220GPC (TOSOH CORPORATION) can be used as a measurement device, and each of TSKgel (registered trademark), Super hzm-M (4.6mmID × 15cm, TOSOH CORPORATION), Super HZ4000(4.6mmID × 15cm, TOSOH CORPORATION), Super HZ3000(4.6mmID × 15cm, TOSOH CORPORATION), and Super HZ2000(4.6mmID × 15cm, TOSOH CORPORATION) can be connected in series as a column, and THF (tetrahydrofuran) can be used as a eluent.

As the measurement conditions, the sample concentration was 0.2 mass%, the flow rate was 0.35ml/min, the sample injection amount was 10 μ L, and the measurement temperature was 40 ℃.

The calibration curve can be obtained using a "standard TSK standard, polystyrene" manufactured by TOSOH CORPORATION: any of 7 samples of "F-40", "F-20", "F-4", "F-1", "A-5000", "A-2500", and "A-1000" was prepared.

The ratio (dispersity) of the number average molecular weight to the weight average molecular weight of the polymer A1 is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

Process for the preparation of Polymer A1

Although the method (synthesis method) for producing the polymer a1 is not particularly limited, it can be synthesized by polymerizing a polymerizable monomer for forming the constituent unit a represented by the formula a, a polymer monomer for forming the constituent unit B having an acid group, and further, if necessary, a polymerizable monomer for forming another constituent unit C in an organic solvent using a polymerization initiator, by way of example. Further, the synthesis can also be performed by a so-called polymer reaction.

In the photosensitive composition layer of the present invention, from the viewpoint of exhibiting good adhesion to the substrate, the polymer component is contained preferably at a ratio of 50 to 99.9% by mass, more preferably at a ratio of 70 to 98% by mass, with respect to the total solid content of the photosensitive composition layer.

In addition, from the viewpoint of exhibiting good adhesion to the substrate, the photosensitive composition layer preferably contains the polymer a1 in an amount of 50 to 99.9 mass%, more preferably 70 to 98 mass%, based on the total solid content of the photosensitive composition layer.

[ other polymers ]

The photosensitive composition layer may contain, as a polymer component, a polymer (sometimes referred to as "other polymer") that does not contain a constituent unit having an acid group protected by an acid-decomposable group, in addition to the polymer a1, within a range that does not impair the effects of the photosensitive transfer material according to the present invention. When the photosensitive composition layer contains another polymer, the amount of the other polymer blended in the total polymer component is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less.

The photosensitive composition layer may contain only 1 type of other polymer, and may contain 2 or more types of other polymers, in addition to the polymer a 1.

As the other polymer, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA2000P, SMA 3000P, SMA 1440 35 1440F, SMA 17352P, SMA 2625P and SMA 3840F (see above, made by Sartomer company, Inc.), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920 and ARUFON UC-3080 (see above, made by TOAGOSEI CO., LTD.), Joncryl 690, Joncryl 678, Joncryl 67 and Joncryl 586 (see above, made by BASF corporation) and the like can be used.

[ photoacid generators ]

The photosensitive composition layer preferably contains a photoacid generator.

The photoacid generator used in the present invention is a compound that can generate an acid by irradiation with radiation such as ultraviolet light, far ultraviolet light, X-rays, and charged particle beams.

The photoacid generator used in the present invention is preferably a compound that generates an acid by sensing an activating light having a wavelength of 300nm or more, preferably 300nm to 450nm, but the chemical structure is not limited. Further, even a photoacid generator which does not directly sense an activation light having a wavelength of 300nm or more can be preferably used in combination with a sensitizer as long as it is a compound which generates an acid by sensing an activation light having a wavelength of 300nm or more with the use of the sensitizer at the same time.

The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and particularly preferably a photoacid generator that generates an acid having a pKa of 2 or less. The lower limit of pKa is not particularly limited, but is preferably at least-10.0, for example.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.

The photoacid generator preferably contains at least 1 compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later, and more preferably contains an oxime sulfonate compound, from the viewpoints of sensitivity and resolution.

Examples of the nonionic photoacid generator include trichloromethyl s-triazine compounds, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, and the like. Among these, from the viewpoint of sensitivity, resolution, and adhesion, the photoacid generator is preferably an oxime sulfonate compound. These photoacid generators can be used alone in 1 kind or in combination of 2 or more kinds. Specific examples of trichloromethyl s-triazine and diazomethane derivatives include compounds described in paragraphs 0083 to 0088 of Japanese patent application laid-open No. 2011-221494.

The oxime sulfonate compound, i.e., the compound having an oxime sulfonate structure, is preferably a compound having an oxime sulfonate structure represented by the following formula (B1).

[ chemical formula 11]

In the formula (B1), R²¹Represents an alkyl group or an aryl group, and represents a bonding site with other atoms or other groups.

Any group of the compound having an oxime sulfonate structure represented by the formula (B1) may be substituted, R²¹The alkyl group in (2) may be linear, may have a branched structure, or may have a cyclic structure. The permissible substituents are explained below.

As R²¹The alkyl group of (2) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. R²¹The alkyl group (C) may be substituted with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (including a bridged alicyclic group such as 7, 7-dimethyl-2-oxonorbornyl group, preferably bicycloalkyl group) or a halogen atom.

As R²¹The aryl group of (1) is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. R²¹The aryl group of (a) may be substituted with 1 or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group and a halogen atom.

The compound having an oxime sulfonate structure represented by the formula (B1) is also preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of japanese patent application laid-open No. 2014-085643.

Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salt compounds, quaternary ammonium salts, and the like. Among these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.

The ionic photoacid generator described in paragraphs 0114 to 0133 of jp 2014-085643 a can also be preferably used as the ionic photoacid generator.

The photoacid generator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

From the viewpoint of sensitivity and resolution, the content of the photoacid generator in the photosensitive composition layer is preferably 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, with respect to the total mass of the photosensitive composition layer.

[ solvent ]

The photosensitive composition layer may contain a solvent.

In order to facilitate the formation of the photosensitive composition layer, the photosensitive composition forming the photosensitive composition layer can be preferably formed by temporarily containing a solvent and adjusting the viscosity of the photosensitive composition, and applying and drying the photosensitive composition containing the solvent.

As the solvent used in the present invention, a known solvent can be used. Examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of Japanese patent application laid-open No. 2011-221494, and these are incorporated herein.

Further, a solvent such as benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, or propylene carbonate may be added to the above solvent as necessary.

The solvent may be used in only 1 kind, or in more than 2 kinds.

The solvent that can be used in the present invention may be used alone in 1 kind, and more preferably, 2 kinds are used simultaneously. When 2 or more solvents are used, for example, propylene glycol monoalkyl ether acetates and dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butanediol alkyl ether acetates are preferably used simultaneously.

The solvent is preferably a solvent having a boiling point of 130 ℃ or higher and less than 160 ℃, a solvent having a boiling point of 160 ℃ or higher, or a mixture of these solvents.

Examples of the solvent having a boiling point of 130 ℃ or higher and less than 160 ℃ include propylene glycol monomethyl ether acetate (boiling point: 146 ℃), propylene glycol monoethyl ether acetate (boiling point: 158 ℃), propylene glycol methyl-n-butyl ether (boiling point: 155 ℃) and propylene glycol methyl-n-propyl ether (boiling point: 131 ℃).

Examples of the solvent having a boiling point of 160 ℃ or higher include ethyl 3-ethoxypropionate (boiling point 170 ℃), diethylene glycol methyl ethyl ether (boiling point 176 ℃), propylene glycol monomethyl ether propionate (boiling point 160 ℃), dipropylene glycol methyl ether acetate (boiling point 213 ℃), 3-methoxybutyl ether acetate (boiling point 171 ℃), diethylene glycol diethyl ether (boiling point 189 ℃), diethylene glycol dimethyl ether (boiling point 162 ℃), propylene glycol diacetate (boiling point 190 ℃), diethylene glycol monoethyl ether acetate (boiling point 220 ℃), dipropylene glycol dimethyl ether (boiling point 175 ℃) and 1, 3-butanediol diacetate (boiling point 232 ℃).

Further, as the solvent, esters, ethers, ketones, and the like described below can be preferably used.

Examples of the esters include ethyl acetate, propyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, isopropyl acetate, and n-butyl acetate.

Examples of the ethers include diisopropyl ether, 1, 4-dioxane, 1, 2-dimethoxyethane, 1, 3-dioxolane, propylene glycol dimethyl ether, and propylene glycol monoethyl ether.

Examples of the ketones include methyl n-butanone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-acetone, and methyl isopropyl ketone.

Examples of the other solvent include toluene, acetonitrile, isopropanol, 2-butanol, and isobutanol.

The content of the solvent in coating the photosensitive composition is preferably 50 to 1,900 parts by mass, more preferably 100 to 900 parts by mass, per 100 parts by mass of the total solid content in the photosensitive composition.

The content of the solvent in the photosensitive composition layer is preferably 2 mass% or less, more preferably 1 mass% or less, and still more preferably 0.5 mass% or less, based on the total mass of the photosensitive composition layer.

[ other additives ]

The photosensitive composition layer in the present invention may contain known additives as needed, in addition to the polymer a1 and the photoacid generator.

Plasticizer-

The photosensitive composition layer may contain a plasticizer for the purpose of improving plasticity.

The plasticizer is preferably a plasticizer having a weight average molecular weight smaller than that of the polymer A1.

From the viewpoint of imparting plasticity, the weight average molecular weight of the plasticizer is preferably 500 or more and less than 10,000, more preferably 700 or more and less than 5,000, and further preferably 800 or more and less than 4,000.

The plasticizer is not particularly limited as long as it is a compound that is compatible with the polymer a1 and exhibits plasticity, and from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

[ chemical formula 12]

In the formula, R is an alkyl group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and x represents a bonding site with other atoms.

For example, even in the case of a compound having an alkyleneoxy group of the above-described structure (referred to as "compound X"), the plasticizer of the present invention is not satisfied when the plasticity of the chemically amplified positive photosensitive composition obtained by mixing the compound X, the polymer a1, and the photoacid generator is not improved as compared with the chemically amplified positive photosensitive composition formed without the compound X. For example, an arbitrarily added surfactant is not generally used in an amount that imparts plasticity to the photosensitive composition, and therefore does not correspond to the plasticizer in the present specification.

Examples of the plasticizer include compounds having the following structures, but are not limited thereto.

[ chemical formula 13]

From the viewpoint of adhesion, the content of the plasticizer is preferably 1 to 50% by mass, and more preferably 2 to 20% by mass, based on the total mass of the photosensitive composition layer.

The photosensitive composition layer may contain only 1 kind of plasticizer, or may contain 2 or more kinds.

Sensitizers-

The photosensitive composition layer may further contain a sensitizer.

The sensitizer absorbs the activating light to become an electron excited state. The sensitizer in the electron excited state is brought into contact with the photoacid generator to cause electron transfer, energy transfer, heat generation, and the like. The photoacid generator chemically changes to decompose and generate an acid.

By containing a sensitizer, exposure sensitivity can be improved.

As the sensitizer, a compound selected from the group consisting of anthracene derivatives, acridone derivatives, thioxanthone derivatives, coumarin derivatives, basic styrene derivatives, and distyrylbenzene derivatives is preferable, and anthracene derivatives are more preferable.

As the anthracene derivative, preferred is anthracene, 9, 10-dibutoxyanthracene, 9, 10-dichloroanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9, 10-dibromoanthracene, 2-ethylanthracene or 9, 10-dimethoxyanthracene.

Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of international publication No. 2015/093271.

The content of the sensitizer is preferably 0 to 10% by mass, more preferably 0.1 to 10% by mass, based on the total mass of the photosensitive composition layer.

Basic compounds-

The photosensitive composition layer preferably further contains a basic compound.

The basic compound can be arbitrarily selected from basic compounds used for chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples of these compounds include the compounds described in paragraphs 0204 to 0207 of Japanese patent application laid-open publication No. 2011-221494, and these contents are incorporated in the present specification.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.

Examples of the aromatic amine include aniline, benzylamine, N-dimethylaniline and diphenylamine.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4, 5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxoquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1, 5-diazabicyclo [4.3.0] -5-nonene, and 1, 8-diazabicyclo [5.3.0] -7-undecene.

Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

Examples of the quaternary ammonium salt of a carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, and the like.

The basic compound can be used alone in 1, or can be used simultaneously in 2 or more.

The content of the basic compound is preferably 0.001 to 5% by mass, and more preferably 0.005 to 3% by mass, based on the total mass of the photosensitive composition layer.

Heterocyclic compounds

The photosensitive composition layer in the present invention may contain a heterocyclic compound.

The heterocyclic compound in the present invention is not particularly limited. For example, the following can be added: in the following, an oxygen-containing monomer such as an epoxy group or an oxetanyl group, an alkoxymethyl group-containing heterocyclic compound, various other cyclic ethers or cyclic esters (lactones), a nitrogen-containing monomer such as a cyclic amine or an oxazoline group, and a heterocyclic monomer having a d-electron such as silicon, sulfur or phosphorus may be added.

When the heterocyclic compound is added, the amount of the heterocyclic compound added to the photosensitive composition layer is preferably 0.01 to 50% by mass, more preferably 0.1 to 10% by mass, and still more preferably 1 to 5% by mass, based on the total mass of the photosensitive composition layer. When the amount is within the above range, the composition is preferable in terms of adhesion and etching resistance. The heterocyclic compounds may be used in a single amount of 1 kind, or in combination of 2 or more kinds.

Specific examples of the compound having an epoxy group in the molecule include bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like.

A compound having an epoxy group in the molecule can be purchased as a commercially available product. Examples thereof include JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Corporation), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like, and commercially available products described in paragraph 0189 of Japanese patent laid-open publication No. 2011-221494.

Other commercially available products include ADEKA RESIN EP-4000S, ADEKA RESIN EP-4003S, ADEKARESIN EP-4010S, ADEKA RESIN EP-4011S (manufactured by ADEKA Corporation, supra), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (manufactured by ADEKA Corporation, supra), DENACOL EX-611, EX-612, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-841, EX-810, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX-121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (above, manufactured by Nagase ChemteX Corporation), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (above, NIPPON STEEL & SUMIKIN CHEMICAL CO., LTD. manufactured) CELLOXIDE 2021P, 2081, 2000, 3000, EHPE3150, Epolead GT400, CELVENUS B0134, B0177 (manufactured by Daicel Corporation) and the like.

The compound having an epoxy group in the molecule may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among the compounds having an epoxy group in the molecule, bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, and aliphatic epoxy resins are more preferable, and aliphatic epoxy resins are particularly preferable.

Specific examples of the compound having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ and PNOX (TOAGOSEI CO., LTD., supra).

Also, the oxetanyl group-containing compound is preferably used alone or in a mixture with an epoxy group-containing compound.

In the photosensitive composition layer in the present invention, the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.

An alkoxysilane compound

The photosensitive composition layer may contain an alkoxysilane compound. As the alkoxysilane compound, a trialkoxysilane compound is preferably cited.

Examples of the alkoxysilane compound include γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, γ -glycidoxypropyltrialkoxysilane, γ -glycidoxypropylalkyldialkoxysilane, γ -methacryloxypropyltrialkoxysilane, γ -methacryloxypropylalkyldialkoxysilane, γ -chloropropyltrialkoxysilane, γ -mercaptopropyltrialkoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrialkoxysilane, and ethylenetrialkoxysilane.

Surfactants-

The photosensitive composition layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, Nonionic (nonionics) or amphoteric can be used, but a preferable surfactant is a Nonionic surfactant.

Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone surfactants, and fluorine surfactants. Further, the following series of trade names can be cited: KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), EFTOP (Japan Electronic money Claim Organization), Megaface (DIC Corporation), Fluorad (Sumitomo 3M Limited), Asahiguard, Surflow (Asahi Glass Co., Ltd.), PolyFox (OMNOVA SOLUTION INC., Ltd.), and SH-8400(Dow Corning Toray Co., Ltd.), etc.

Further, as the surfactant, a copolymer containing a constitutional unit SA and a constitutional unit SB represented by the following formula I-1 and having a weight average molecular weight (Mw) as measured by gel permeation chromatography in terms of polystyrene, which is measured by gel permeation chromatography using Tetrahydrofuran (THF) as a solvent, of 1,000 to 10,000 can be exemplified as a preferable example.

[ chemical formula 14]

In the formula (I-1), R⁴⁰¹And R⁴⁰³Each independently represents a hydrogen atom or a methyl group, R⁴⁰²Represents a linear alkylene group having 1 to 4 carbon atoms, R⁴⁰⁴Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are percentages by mass of the polymerization ratio, p represents a numerical value of 10 to 80 mass%, q represents a numerical value of 20 to 90 mass%, and r represents 1 to 118 or less, s represents an integer of 1 to 10 inclusive, and represents a bonding site with another structure.

L is preferably a branched alkylene group represented by the following formula (I-2). R in the formula (I-2)⁴⁰⁵An alkyl group having 1 to 4 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably an alkyl group having 2 or 3 carbon atoms, from the viewpoint of compatibility and wettability with respect to the surface to be coated. The sum of p and q (p + q) is preferably 100% by mass, i.e., 100% by mass.

[ chemical formula 15]

The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

The surfactant described in paragraph 0017 of japanese patent No. 4502784 and paragraphs 0060 to 0071 of japanese patent application laid-open No. 2009-237362 can also be used.

The surfactant may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The amount of the surfactant added is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and still more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive composition layer.

Other ingredients-

The photosensitive composition layer of the present invention may further contain known additives such as metal oxide particles, antioxidants, dispersants, acid proliferators, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, ultraviolet absorbers, tackifiers, crosslinking agents, and organic or inorganic anti-settling agents.

Preferred embodiments of the other components are described in paragraphs 0165 to 0184 of Japanese patent application laid-open No. 2014-085643, the contents of which are incorporated in the present specification.

[ method for Forming photosensitive composition layer ]

The photosensitive composition for forming the photosensitive composition layer can be prepared by mixing the respective components and the solvent at an arbitrary ratio and by an arbitrary method, and stirring and dissolving the mixture. For example, a composition can be prepared by dissolving each component in a solvent in advance and mixing the obtained solutions at a predetermined ratio. The composition prepared as above can also be used after being filtered using a filter having a pore size of 0.2 μm or the like.

In order to improve the uniformity of film thickness, the unevenness of surface state, and the like of the photosensitive composition layer, the solid components (for example, the polymer component, the photoacid generator, the basic compound, and the surfactant) in the photosensitive composition used in the present invention are preferably adjusted by dissolving in the solvent.

The photosensitive composition layer can be formed by applying the photosensitive composition onto the temporary support and drying the applied photosensitive composition.

Further, after another layer described later is formed on the temporary support, the photosensitive composition layer may be applied.

< Positive photosensitive transfer Material >

Hereinafter, the positive photosensitive transfer material used in the present invention (hereinafter, also simply referred to as "photosensitive transfer material") will be described in detail.

Fig. 2 schematically shows an example of the layer structure of the photosensitive transfer material used in the present invention. The photosensitive transfer material 100 shown in fig. 2 is formed by laminating a temporary support 12, a positive photosensitive composition layer 14, and a cover film 16 in this order.

The positive photosensitive composition layer 14 contains a polymer containing a constituent unit having an acid group protected by an acid-decomposable group and a photoacid generator.

Hereinafter, the constituent materials of the photosensitive transfer material used in the present invention will be described. The above-described configuration of the present invention is sometimes referred to as follows in the present specification.

Temporary support

The temporary support is a support that supports the positive photosensitive composition layer and can be detached from the positive photosensitive composition layer.

The temporary support used in the present invention preferably has light-transmitting properties from the viewpoint that the photosensitive composition layer can be exposed through the temporary support when the photosensitive composition layer is subjected to pattern exposure.

The term "having light transmittance" means that the transmittance of the dominant wavelength of light used in pattern exposure is 50% or more, and from the viewpoint of improving exposure sensitivity, the transmittance of the dominant wavelength of light used in pattern exposure is preferably 60% or more, and more preferably 70% or more. As a method for measuring the transmittance, a method of measuring by MCPD Series manufactured by Otsuka Electronics co.

Examples of the temporary support include a glass substrate, a resin film, and paper, and the resin film is particularly preferable from the viewpoint of strength, flexibility, and the like. Examples of the resin film include a cycloolefin polymer film, a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, from the viewpoint of optical characteristics and low moisture permeability, a film containing a cycloolefin polymer is preferable, and a cycloolefin polymer film is particularly preferable.

The thickness of the temporary support is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm from the viewpoint of ease of handling, versatility, and the like.

The thickness of the temporary support may be selected according to the material, from the viewpoints of the strength of the support, the flexibility required for bonding to the circuit wiring forming substrate, the light transmittance required in the first exposure step, and the like.

A preferred embodiment of the temporary support is described in paragraphs 0017 to 0018 of japanese patent application laid-open No. 2014-085643, and the contents of this publication are incorporated in the present specification.

Other layers-

The photosensitive transfer material used in the present invention may have a layer other than the photosensitive composition layer (hereinafter, may be referred to as "other layer"). Examples of the other layers include a contrast reinforcing layer, an intermediate layer, a cover film, and a thermoplastic resin layer.

[ contrast enhancement layer ]

The photosensitive transfer material used in the present invention may have a contrast enhancing layer in addition to the photosensitive composition layer.

The Contrast Enhancement Layer (CEL) is a Layer containing a material (referred to as a photoactivatable pigment component) which absorbs light of a large wavelength before exposure but gradually decreases as it is exposed, that is, which has a high light transmittance. As the photobleaching pigment component, a diazonium salt, a styrylpyridinium (stilbazolium) salt, an arylnitroso salt, and the like are known. As the coating forming component, a phenolic resin or the like is used.

Further, as the contrast enhancement layer, materials described in paragraphs 0004 to 0051 of japanese patent application laid-open No. 6-097065, paragraphs 0012 to 0055 of japanese patent application laid-open No. 6-332167, a photopolymer manual, editorial series of photopolymerization seminars, industrial examination (1989), photopolymerization Technology (Technology), editorial series of shanggang and pinsun, THE NIKKAN kogyoshimben, ltd. (1988) can be used.

[ intermediate layer ]

The photosensitive composition layer may be provided with an intermediate layer for the purpose of coating a plurality of layers and preventing mixing of components during storage after coating.

As the intermediate layer, the intermediate layers described in paragraphs 0084 to 0087 of Japanese patent application laid-open No. 2005-259138 can be used. The intermediate layer is preferably an intermediate layer dispersed or dissolved in water or an aqueous alkali solution.

Examples of the material for the intermediate layer include polyvinyl alcohol-based resins, polyvinyl pyrrolidone-based resins, cellulose-based resins, acrylamide-based resins, polyethylene oxide-based resins, gelatin, vinyl ether-based resins, polyamide resins, and copolymers thereof. Among these, a combination of polyvinyl alcohol and polyvinylpyrrolidone is particularly preferable.

[ thermoplastic resin layer, cover film, etc. ]

The photosensitive transfer material used in the present invention may have a thermoplastic resin layer between the temporary support and the photosensitive composition layer from the viewpoint of transferability.

The photosensitive transfer material according to the present invention may further include a cover film for protecting the photosensitive composition layer.

Preferable embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of jp 2014-085643 a, and preferable embodiments of the other layer are described in paragraphs 0194 to 0196 of jp 2014-085643 a, the contents of which are incorporated in the present specification.

Among them, the thermoplastic resin layer preferably contains at least 1 thermoplastic resin selected from the group consisting of acrylic resins and styrene/acrylic copolymers from the viewpoint of transferability.

When the photosensitive transfer material used in the present invention has another layer such as a thermoplastic resin layer, it can be produced according to the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of jp 2006-a-259138.

For example, in the case of producing the photosensitive transfer material of the present invention having a thermoplastic resin layer and an intermediate layer, a solution (coating liquid for the thermoplastic resin layer) in which a thermoplastic organic polymer and an additive are dissolved is applied onto a temporary support and dried to form the thermoplastic resin layer, and then a preparation liquid (coating liquid for the intermediate layer) prepared by adding a resin and an additive to a solvent in which the thermoplastic resin layer is not dissolved is applied onto the obtained thermoplastic resin layer and dried to laminate the intermediate layer. The photosensitive transfer material according to the present invention can be preferably produced by further applying a photosensitive composition prepared using a solvent that does not dissolve the intermediate layer on the formed intermediate layer, and drying the photosensitive composition to laminate the photosensitive composition layer.

(input device and display device)

An input device is an example of a device provided with a circuit board manufactured by the method for manufacturing a circuit board according to the present invention.

The input device in the present invention is preferably an electrostatic capacitance type touch panel.

The display device of the present invention preferably includes the input device of the present invention.

The display device of the present invention is preferably an image display device such as an organic EL display device or a liquid crystal display device.

(touch Panel and touch Panel display device and method for manufacturing the same)

The touch panel according to the present invention is a touch panel including at least a circuit board manufactured by the method for manufacturing a circuit board according to the present invention. The touch panel according to the present invention preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.

The touch panel display device according to the present invention is a touch panel display device including at least a circuit board manufactured by the method for manufacturing a circuit board according to the present invention, and is preferably a touch panel display device including a touch panel according to the present invention.

The method for manufacturing a touch panel or a touch panel display device according to the present invention preferably includes the method for manufacturing a circuit board according to the present invention.

The method for manufacturing a touch panel or a touch panel display device according to the present invention preferably includes the steps of: a step of bonding the photosensitive composition layer of the photosensitive transfer material obtained by the method for producing a photosensitive transfer material, in contact with the substrate; a step of pattern-exposing the photosensitive composition layer of the photosensitive transfer material after the step of bonding; a step of forming a pattern by developing the photosensitive composition layer after the step of exposing; and a step of etching the substrate in the region where the pattern is not arranged. The details of each step are the same as those of each step in the above-described method for manufacturing a circuit board, and preferred embodiments are the same.

The touch panel according to the present invention and the detection method in the touch panel display device according to the present invention may be any of known methods such as a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among them, the electrostatic capacitance system is preferable.

Examples of Touch panel types include a so-called in-cell type (described in, for example, fig. 5, 6, 7, and 8 of japanese unexamined patent publication No. 2012-517051), a so-called out-cell type (described in, for example, fig. 19 of japanese unexamined patent publication No. 2013-168125, fig. 1 and 5 of japanese unexamined patent publication No. 2012-089102), an OGS (One Glass Solution, One-Touch) type, a TOL (Touch-on-Lens) type (described in, for example, fig. 2 of japanese unexamined patent publication No. 2013-054727), other structures (described in, for example, fig. 6 of japanese unexamined patent publication No. 2013-164871), and various out-cell types (described in, for example, GG, G1-G2, GFF, GF2, GF1, G1F).

The touch panel according to the present invention and the touch panel display device according to the present invention can be applied to a configuration disclosed in "latest touch panel technology" (published in 2009, 6 th, Techno Times co., ltd.), samaoguangdi's republic of "technology and development of touch panel", CMC publication (2004, 12), FPD International 2009Forum T-11 lecture textbook, Cypress Semiconductor Corporation application note AN2292, and the like.

Examples

The following examples are provided to more specifically describe embodiments of the present invention. The materials, amounts used, ratios, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the embodiment of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

[ (A) Polymer component ]

In the following synthetic examples, the following abbreviations respectively represent the following compounds.

ATHF: acrylic acid 2-tetrahydrofurfuryl ester (synthetic product)

AA: acrylic acid (Tokyo Chemical Industry Co., Ltd.)

MAA: methacrylic acid (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

EA: ethyl acrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

MMA: methyl methacrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

CHA: cyclohexyl acrylate (Tokyo Chemical Industry Co., Ltd.; manufactured by Ltd.)

MATHF: 2-tetrahydrofurfuryl methacrylate (synthetic)

ATHP: acrylic acid 2-tetrahydrofuran ester (Shin-Nakamura Chemical Co., Ltd., manufactured by Ltd.)

MAEVE: methacrylic acid 1-ethoxyethyl ester (synthetic product)

PMPMPMMA: 1,2,2,6, 6-pentamethyl-4-methylpiperidine methacrylate (manufactured by FUJIFILM Wako Pure chemical corporation)

PGMEA: propylene glycol monomethyl ether acetate (manufactured by SHOWA DENKO K.K.)

V-601: dimethyl 2, 2' -azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries, Ltd.)

< Synthesis of ATHF >

Acrylic acid (72.1g, 1.0mol), hexane (72.1g) was added to the 3-neck flask and cooled to 20 ℃. Camphorsulfonic acid (7.0mg, 0.03mmol) and 2-dihydrofuran (77.9g, 1.0mol) were added dropwise thereto, and after stirring at 20 ℃. + -. 2 ℃ for 1.5 hours, the temperature was raised to 35 ℃ and stirring was carried out for 2 hours. KYOWARD 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry co., ltd.) and KYOWARD 1000 (filter material, hydrotalcite-based powder, manufactured by Kyowa Chemical Industry co., ltd.) were sequentially overlaid on a Nutsche suction filter, and then the reaction solution was filtered to obtain a filtrate. Hydroquinone monomethyl ether (MEHQ, 1.2mg) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ℃ to obtain 140.8g (yield 99.0%) of tetrahydrofuran-2-yl acrylate (ath) as a colorless oil.

< Synthesis of MATHF >

The synthesis was performed in the same manner as the synthesis of ATHF, except that acrylic acid was changed to methacrylic acid.

< Synthesis of MAEVE >

The synthesis was carried out according to the method described in paragraph 0139 of Japanese patent application laid-open No. 2007-163772.

< Synthesis example of Polymer A-1 >

PGMEA (75.0g) was placed in a 3-neck flask, and the temperature was raised to 90 ℃ under a nitrogen atmosphere. A solution to which ATHF (40.0g), AA (2.0g), ethyl acrylate (EA, 20.0g), methyl methacrylate (MMA, 22.0g), cyclohexyl acrylate (CHA, 16.0g), V-601(4.0g) and PGMEA (75.0g) were added was added dropwise over 2 hours to a solution in a 3-necked flask maintained at 90 ℃. + -. 2 ℃. After completion of the dropwise addition, the mixture was stirred at 90 ℃. + -. 2 ℃ for 2 hours, whereby polymer A-1 (solid content concentration: 40.0%) was obtained.

[ Table 1]

< Synthesis of polymers A2-A10 >

The synthesis was performed in the same manner as for the polymer a1 under the other conditions, with the types of monomers changed as shown in table 2 below. The solid content concentration of the polymer a was set to 40 mass%. The unit of the amount of each monomer used in table 2 is mass%.

[ Table 2]

< Synthesis of Polymer A-11(PHS-EVE) >

According to the method described in paragraph 0232 of Japanese patent laid-open No. 2014-085643, polymer A-11 was obtained.

[ chemical formula 16]

< Synthesis of Polymer A-12 (Novolac-EVE) >

According to the method described in paragraph 0234 of Japanese patent laid-open No. 2014-085643, polymer A-12 was obtained.

[ chemical formula 17]

[ (B) photoacid generators ]

B-1: the following structure (the compound described in paragraph 0227 of Japanese patent laid-open publication No. 2013-47765, synthesized according to the method described in paragraph 0227.)

[ chemical formula 18]

B-2: PAG-103 (trade name, manufactured by BASF corporation, the following compound)

[ chemical formula 19]

B-3: a compound having a structure shown below (synthesized according to the method described in paragraph 0210 of Japanese patent laid-open No. 2014-197155.)

[ chemical formula 20]

In the above compounds, Ts represents a tosyl group.

B-4: GSID-26-1 triarylsulfonium salt (available from BASF corporation, the following compounds)

[ chemical formula 21]

[ (C) surfactant ]

C-1: a compound of the structure shown below

[ chemical formula 22]

[ (D) basic Compound ]

D-1: a compound of the structure shown below

[ chemical formula 23]

< naphthoquinone diazide >)

TS-200TF (TOYO Gosei Co., Ltd., a compound having the following structure)

[ chemical formula 24]

< preparation of photosensitive transfer Material >

In example 1 and comparative example 1, a polymer component, a photoacid generator, a basic compound, and a surfactant were dissolved and mixed in PGMEA so that the solid content concentration became 10 mass%, and filtration was performed through a polytetrafluoroethylene filter having a pore diameter of 0.2 μm, to obtain a photosensitive composition, so as to obtain a solid content ratio shown in table 3 below.

The photosensitive composition was applied to a 30 μm thick polyethylene terephthalate film (hereinafter referred to as pet (a)) as a temporary support using a slit nozzle so that the dry film thickness was 3.0 μm and the application width was 1.0 m. Then, the resultant was passed through a drying zone at 80 ℃ for 40 seconds, and finally, a polyethylene film (Tredegar co., ltd., OSM-N) was pressed as a cover film to prepare a photosensitive transfer material 1.

Further, the total haze of PET (A) was 0.19%. Regarding the film haze, the total haze value (%) of the base sheet was measured using a Suga Test instruments Co., Ltd. haze tester HZ-2 in accordance with JIS-K-7136.

< evaluation of Properties >

A PET substrate was used in which ITO was deposited on a 100 μm thick PET substrate at a thickness of 150nm by sputtering, and copper was deposited thereon at a thickness of 200nm by vacuum evaporation.

< evaluation of sensitivity >

The prepared photosensitive transfer material was laminated on a PET substrate on which ITO and copper were sequentially formed under lamination conditions of a roll temperature of 120 ℃, a linear pressure of 0.8MPa, and a linear velocity of 1.0m/min, to prepare a sample.

The temporary support was not peeled off, and was exposed to light through a line width-to-pitch pattern mask (Duty ratio 1:1) having a line width of 3 to 20 μm using an ultra-high pressure mercury lamp, left for 1 hour, and then peeled off and developed. Development was carried out using a 1.0% aqueous solution of sodium carbonate at 25 ℃ for 30 seconds by shower development. When a pattern with a line width and a pitch of 20 μm was formed by the above method, the residue in the space portion was observed and evaluated by a Scanning Electron Microscope (SEM), and the exposure amount without residue was determined. The exposure is less than 200mJ/cm²At a level that can be practical.

5: less than 80mJ/cm²

4：80mJ/cm²Above and less than 150mJ/cm²

3：150mJ/cm²Above and less than 200mJ/cm²

2：200mJ/cm²Above and less than 300mJ/cm²

1：300mJ/cm²The above

< evaluation of resolution >

The temporary support was not peeled off, and was exposed to light through a line width-to-pitch pattern mask (Duty ratio 1:1) having a line width of 3 to 20 μm using an ultra-high pressure mercury lamp, left for 1 hour, and then peeled off and developed. Development was carried out using a 1.0% aqueous solution of sodium carbonate at 25 ℃ for 30 seconds by shower development. Among the line width and pitch patterns thus obtained, the pattern of the highest resolution is set as the final resolution. When the final resolution is determined, if the sidewall of the pattern has a large roughness, the pattern is not resolved.

5: less than 6 μm

4.5: less than 8 μm and 6 μm or more

4: less than 10 μm and 8 μm or more

3: less than 15 μm and 10 μm or more

2: less than 20 μm and 15 μm or more

1: 20 μm or more

< evaluation of removability >

The temporary support was not peeled off, and was exposed to light through a line width-to-pitch pattern mask (Duty ratio 1:1) having a line width of 3 to 20 μm using an ultra-high pressure mercury lamp, left for 1 hour, and then peeled off and developed. Development was carried out using a 1.0% aqueous solution of sodium carbonate at 25 ℃ for 30 seconds by shower development. Next, the copper layer was etched for 60 seconds by a dipping method using a 25 ℃ copper etching solution (KANTO CHEMICAL co., manufactured by inc., product Cu-02), and then the ITO layer was etched for 60 seconds by a dipping method using a 25 ℃ ITO etching solution (KANTO CHEMICAL co., manufactured by inc., product ITO-02). The same operation was performed using copper and an ITO etchant for the material that was not resolved in the above-described resolution evaluation (evaluation 1).

The residual photosensitive composition layer is removed using a removing liquid. For the removal, a 50 ℃ aqueous removal liquid (10% organic base, water 90% water dilution of BONDERITE C-AK P123 manufactured by Henkel Japan Ltd.) and ED-1200 manufactured by MIKASA CO., LTD were used for the removal by spraying. In this case, the same experiment was performed on the start date of use of the removing solution (0 day), or 3 days, 7 days, 14 days, 21 days, or 28 days from the start date of use, with the apparatus operating time of 1 day set to 6 hours.

In the case of performing blanket exposure before removal, exposure was performed at the exposure amount before peeling described in table 3 using an ultra-high pressure mercury lamp without passing through a pattern mask, and the removal test was performed after leaving for 10 seconds after exposure.

The photosensitive composition layer was observed by a Scanning Electron Microscope (SEM), and the time during which the photosensitive composition layer on the copper layer could be completely removed was determined. When the removability is judged, it is preferable that the removal time is less than 70 seconds, which is a practical level.

[ evaluation criteria ]

4: removing time is below 20 seconds

3: the removing time is more than 20 seconds and less than 70 seconds

2: the removing time is more than 70 seconds and less than 300 seconds

1: can not be removed

The evaluation results are shown in table 3 below.

[ Table 3]

As shown in table 3, the method for manufacturing the circuit board according to the example was excellent in removability even when the removing liquid was used for a long time.

(example 101)

On a 100 μm thick PET substrate, ITO was formed as a2 nd conductive layer with a thickness of 150nm by sputtering, and on the top, copper was formed as a1 st conductive layer with a thickness of 200nm by vacuum evaporation, thereby producing a circuit forming substrate.

The photosensitive transfer material 1 obtained in example 1 was laminated on the copper layer (roll temperature 120 ℃, line pressure 0.8MPa, line speed 1.0 m/min.). The contact pattern exposure was performed using a photomask provided with a pattern a shown in fig. 3 having a structure in which conductive layer pads are connected in one direction without peeling the temporary support. Then, the temporary support was peeled off, and development and water washing were performed to obtain pattern a. Next, the copper layer was etched using a copper etching solution (KANTO CHEMICAL co., manufactured by inc., product Cu-02), and then, the ITO layer was etched using an ITO etching solution (KANTO CHEMICAL co., manufactured by inc., product ITO-02), thereby obtaining a substrate in which both copper and ITO are depicted in a pattern a.

Next, pattern exposure, development, and washing were performed using a mask in which the openings of the pattern B shown in fig. 4 were provided in an aligned state.

Then, the copper layer was etched using Cu-02, and the remaining photosensitive composition layer was blanket-exposed by an ultra-high pressure mercury lamp (300 mJ/cm)²) After leaving for 10 seconds after the exposure, the resist was removed with a removing liquid (BONDERITE C-AK P123 manufactured by Henkel Japan Ltd.) to obtain a circuit board.

The obtained circuit board was observed with a microscope, and was a fine pattern without peeling, chipping, or the like.

(example 102)

The photosensitive transfer material 1 obtained in example 1 was laminated on the copper layer (roll temperature 120 ℃, line pressure 0.8MPa, line speed 1.0 m/min.).

Pattern exposure was performed using a photomask provided with a pattern a shown in fig. 3 having a structure in which conductive layer pads are connected in one direction without peeling the temporary support. Then, the temporary support was peeled off, and development and water washing were performed to obtain pattern a. Next, the copper layer was etched using a copper etching solution (KANTO CHEMICAL co., manufactured by inc., product Cu-02), and then, the ITO layer was etched using an ITO etching solution (KANTO CHEMICAL co., manufactured by inc., product ITO-02), thereby obtaining a substrate in which both copper and ITO are depicted in a pattern a.

Subsequently, pet (a) was laminated on the remaining resist as a protective layer. In this state, pattern exposure was performed using a photomask in which the openings of the pattern B shown in fig. 4 were provided in an aligned state, and pet (a) was peeled off, followed by development and water washing.

Then, the copper layer was etched using Cu-02, and the remaining photosensitive composition layer was blanket-exposed by an ultra-high pressure mercury lamp (300 mJ/cm)²) And is placed after exposureAfter 10 seconds, the substrate was removed with a removing solution (BONDERITE C-AK P123 manufactured by Henkel Japan Ltd.) to obtain a circuit board.

(example 2)

The photosensitive transfer material 1 obtained in example 1 was patterned into a substrate by the method described in paragraph 0199. The removal property was evaluated in the same manner as in example 1, except that the photosensitive composition was heated at a substrate temperature of 60 ℃ for 5 seconds by an IR heater and left to stand after blanket exposure before peeling. The evaluation results are shown in table 4.

(example 3)

The removability was evaluated by the same method as in example 2, except that the substrate temperature in the heating step was changed to 25 ℃. The evaluation results are shown in table 4.

[ Table 4]

As a result, by performing the heating step, the removal performance equivalent to or higher than that of example 1 was obtained even if the standing time after exposure was short.

As shown in table 4, the method for manufacturing the circuit board of example 2 was excellent in removability even when the removing liquid was used for a long period of time, for example, 21 days or 28 days.

(example 4)

Pattern exposure was performed using a photomask provided with a pattern a shown in fig. 3 having a structure in which conductive layer pads are connected in one direction without peeling the temporary support. Then, the temporary support was peeled off, and development and water washing were performed to obtain pattern a. Next, the copper layer was etched and washed with water using a copper etching solution (KANTO CHEMICAL co., product of inc., Cu-02) to obtain copper wiring depicted as a pattern a. Further, the substrate after copper etching was subjected to etching of the ITO layer using an ITO etching solution (ITO-02 manufactured by INC.) and finally cleaning with a rinse solution (a 0.1 wt% aqueous solution of a surfactant, a surfactant: Megaface F-444 (manufactured by DIC CORPORATION)), thereby obtaining a substrate in which both copper and ITO were drawn in the pattern A.

The substrate was subjected to blanket exposure (300 mJ/cm) by an ultra-high pressure mercury lamp²) After exposure, the substrate was heated at 60 ℃ for 5 seconds by an IR heater and left to stand, and then the removal performance of the photosensitive resin layer was evaluated by the same method as in example 1. As the removing solution, BONDERITE C-AK P123 (manufactured by Henkel Japan Ltd.) was used. In the procedure of this example, as shown in table 5 below, good removal performance was also obtained.

[ Table 5]

(example 5)

Pattern exposure was performed using a photomask provided with a pattern a shown in fig. 3 having a structure in which conductive layer pads are connected in one direction without peeling the temporary support. Then, the temporary support was peeled off, and development and water washing were performed to obtain pattern a. Next, the copper layer was etched and washed with water using a copper etching solution (KANTO CHEMICAL co., product of inc., Cu-02) to obtain copper wiring depicted as a pattern a. Further, the substrate after copper etching was subjected to ITO etching using an ITO etching solution (ITO-02 manufactured by inc.) and cleaned using a rinse solution 1 having the following composition, and then water was completely blown off by a blower, thereby obtaining a substrate in which both copper and ITO are drawn in a pattern a.

The substrate was subjected to blanket exposure (300 mJ/cm) by an ultra-high pressure mercury lamp²) After exposure, the substrate was heated at 60 ℃ for 5 seconds by an IR heater and left to stand, and then the removal performance of the photosensitive resin layer was evaluated. As the removing solution, BONDERITE C-AK P123 (manufactured by Henkel Japan Ltd.) was used. The evaluation results are shown in tables 6 and 7.

< rinse solution 1 >

Ion-exchanged water: 9,990 parts

Polyoxyethylene (10) octylphenyl ether (manufactured by FUJIFILM Wako Pure Chemical Corporation): 5 portions of

Polyoxyethylene polyoxypropylene glycol (160 ethylene oxide (E.O.) (30 propylene oxide (P.O.) (manufactured by FUJIFILMWako Pure Chemical Corporation): 5 portions of

(example 6)

The removal performance of the photosensitive resin layer was evaluated in the same manner as in example 5, except that the rinse solution after ITO etching was changed to rinse solution 2 described below. The evaluation results are shown in tables 6 and 7.

< rinse solution 2 >

Ion-exchanged water: 9,985 parts

Polyoxyethylene (10) octylphenyl ether: 5 portions of

Polyoxyethylene polyoxypropylene glycol (160E.O.) (30 P.O.): 5 portions of

3-methoxy-3-methylbutanol: 5 portions of

[ Table 6]

[ Table 7]

As a result, even when the heating step is performed using the rinse solution 1 or the rinse solution 2 as the rinse solution after ITO etching, good removal performance can be obtained.

(examples 7 to 19)

Photosensitive transfer materials were prepared in the same manner as in example 1, except that the compositions of the photosensitive compositions shown in table 8 below were used. Sensitivity evaluation and resolution evaluation were performed by the same method as in example 1, and removal evaluation was performed by the same method as in example 2 except that the exposure amount before peeling, the heating time in the heating step, and the heating temperature were changed. The evaluation results are shown in table 8.

As shown in table 8, the method for manufacturing the circuit board according to the example was excellent in removability even when the removing liquid was used for a long time.

Description of the symbols

12-temporary support, 14-positive photosensitive composition layer, 14A-1 st pattern, 14B-2 nd pattern, 16-cover film, 20-substrate for circuit wiring formation, 22-substrate, 24-1 st conductive layer, 24A-1 st conductive layer (after 1 st etching step), 24B-1 st conductive layer (after 2 nd etching step), 26-2 nd conductive layer, 26A-2 nd conductive layer (after 1 st etching step and 2 nd etching step), 30-mask, 40-mask, 100-photosensitive transfer material, S, SL-solid line portion, G-gray portion, DL-dotted line portion.

Claims

1. A method of manufacturing a circuit substrate, comprising in order:

forming a positive photosensitive composition layer on the conductive layer;

pattern-exposing the positive photosensitive composition layer;

developing the pattern-exposed positive photosensitive composition layer;

etching the conductive layer using the developed positive photosensitive composition layer as a mask;

a step of blanket-exposing the developed positive photosensitive composition layer; and

and removing the blanket-exposed positive photosensitive composition layer.

2. The method of manufacturing a circuit substrate according to claim 1,

3. The method of manufacturing a circuit substrate according to claim 1 or 2,

4. The method of manufacturing a circuit substrate according to any one of claims 1 to 3,

the positive photosensitive composition layer contains a polymer and a photoacid generator, and the polymer contains a constituent unit having an acid group protected by an acid-decomposable group.

5. The method of manufacturing a circuit substrate according to claim 4,

the constituent unit having an acid group protected with an acid-decomposable group is a constituent unit represented by any of the following formulae A1 to A3,

in the formula A1, R¹¹And R¹²Each independently represents a hydrogen atom, an alkyl group orAryl radical, at least R¹¹And R¹²Is alkyl or aryl, R¹³Represents alkyl or aryl, optionally R¹¹Or R¹²And R¹³Linked to form a cyclic ether, R¹⁴Represents a hydrogen atom or a methyl group, X¹Represents a single bond or a 2-valent linking group, R¹⁵Represents a substituent, n represents an integer of 0 to 4,

in the formula A2, R²¹And R²²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R²¹And R²²Is alkyl or aryl, R²³Represents alkyl or aryl, optionally R²¹Or R²²And R²³Linked to form a cyclic ether, R²⁴Each independently represents a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, m represents an integer of 0 to 3,

in the formula A3, R³¹And R³²Each independently represents a hydrogen atom, an alkyl group or an aryl group, at least R³¹And R³²Is alkyl or aryl, R³³Represents alkyl or aryl, optionally R³¹Or R³²And R³³Linked to form a cyclic ether, R³⁴Represents a hydrogen atom or a methyl group, X⁰Represents a single bond or a 2-valent linking group.

6. The method of manufacturing a circuit substrate according to claim 5,

7. The method of manufacturing a circuit substrate according to any one of claims 1 to 6,

8. The method of manufacturing a circuit substrate according to any one of claims 1 to 7,

the conductive layer is a copper layer.

9. The method of manufacturing a circuit substrate according to any one of claims 1 to 8,

10. The method of manufacturing a circuit substrate according to claim 9,

the temporary support is a resin film.

11. The method of manufacturing a circuit substrate according to claim 9 or 10,

the temporary support comprises a cyclic olefin polymer.

12. A method for manufacturing a touch panel, comprising the method for manufacturing a circuit substrate according to any one of claims 1 to 11.